【作者】 梁爽；

【导师】 徐吉静；

【作者基本信息】 吉林大学 ， 无机化学， 2025， 博士

【摘要】 锌空气电池因负极材料锌含量丰富且成本较低,同时兼具高安全性,在储能与便携电源等领域极具应用潜力。然而,由于空气正极反应动力学迟缓,导致电池极化现象显著,在倍率性能、循环稳定性及能量转换效率等关键指标上,与产业化要求仍存在明显差距。研究表明,通过外场辅助策略可有效扩展反应界面,促进电荷传输,显著提升电池的能量转化效率与循环寿命。目前,在构建高性能光辅助锌空气电池过程中,亟待解决光电正极导电性不足、氧气吸附能垒较高、电子-空穴复合速率过快、光电转换效率低以及电解液易蒸发等问题。为此,开发具有优异导电性与高效光生电荷分离能力及多场耦合响应的新型光电正极材料成为研究重点,其关键在于维持较高的载流子分离效率,促进光生电子与氧气的充分接触,实现快速的氧活化与电荷转移。目前,研究者通过纳米结构调控与异质结构建等策略已取得显著进展,但在光电转换效率方面仍存在较大提升空间。此外,针对光照条件下电解液蒸发的问题,应开发具有电解液循环功能的多场耦合辅助电池系统,通过合理利用外部能量场实现光生载流子的持续分离,为构建经济高效的新型锌空气电池体系提供重要技术支撑。基于以上问题,本论文主要围绕光辅助锌空气电池正极的开发与外场辅助策略的合理整合利用,开展了以下研究工作:1.从结构设计出发,利用限域空间结构改善光生载流子的分离效率。受到管状限域空间可调控电荷分布的启发,开发了基于二硫化钼（Mo S₂）半导体的一维限域通道（Mo S₂-ONT）,揭示了通道中光生载流子快速分离和传输机制,并构筑了高性能光辅助锌空气电池。相比于抑制光催化剂中载流子快速复合的经典策略,本工作所制备的Mo S₂管状限域空间可以实现高效的载流子分离,延长载流子寿命。Mo S₂-ONT表现出较高的表面光电压,促进更多的光生电子参与反应,具有优异的光催化效果。相关的电化学测试和理论计算结果进一步表明,Mo S₂-ONT具有更快的传质行为和更高的氧还原催化效率。此外,Mo S₂-ONT光电正极在锌空气电池中展现出优异的倍率性能、功率密度和循环寿命。该工作验证了限域载流子分离策略在光辅助锌空气电池中的实用性,为发展下一代低成本高性能的光辅助储能技术提供了新视角和关键材料。2.从外场协同作用出发,利用低能力场产生压电效应促进光生载流子持续分离。受到光场与其他外场耦合可增强光生电子-空穴自发分离和传输动力的启发,开发了一种光场与力场耦合的锌空气电池,将力场引发的压电效应引入到光辅助锌空气电池中。使用循环电解液减缓了光照下的蒸发,同时液体流动产生的机械力可作为压力源激发压电效应。此外,受到藤蔓植物在风中卷曲性质的启发,设计了一种微螺旋结构的压电-光响应催化剂三氧化二铁@聚偏氟乙烯-三氟乙烯（Fe@P（V-T））。通过流动电解液使正极产生周期性形变,不断重构内置电场,促进载流子的持续分离。得益于重构的内置电场对氧还原/氧析出反应动力学的提升,在电解液循环产生的微振动条件下光辅助锌空气电池的充放电过电位显著降低,功率密度提高了3.2倍。本研究为压电效应与光-力耦合辅助策略在能量存储领域的应用提供了深入的理解,并为多场耦合辅助锌空气电池的研究开辟了新的视角。3.从电荷传输通道设计出发,利用光场辅助调控近中性锌空气电池反应动力学。受到光辅助策略在提升光电正极反应动力学方面的显著效果启发,开发了一种基于光响应分子筛材料的近中性锌空气电池,设计了钌修饰的钛硅分子筛（Ru@TS@C）作为光催化剂。将光场引入到近中性锌空气电池中,有效解决了中性环境下反应动力学缓慢的问题。通过光谱测试、光电测试及理论计算,揭示了Ru@TS@C的光响应活性及其在导电分子筛中的光生电荷传输机制与氧还原反应机理。基于Ru@TS@C的光辅助近中性锌空气电池表现出优异的4e^-路径氧还原选择性和高度可逆性,显著提升了正极反应动力学。实验结果表明,在0.2 m A cm^-2的电流密度下,光辅助条件下的过电位仅为218 m V,远低于黑暗条件下的844 m V。这一研究不仅为分子筛在光辅助锌空气电池中的应用开辟了新的研究方向,而且为高性能光辅助电池的设计与开发提供了重要的理论依据和实践指导。本论文促进了对锌空气电池中光辅助和多场耦合策略的理解,为下一代储能技术提供了创新解决方案。更多还原

【Abstract】 Zn-air batteries have shown great application potential in the fields of energy storage and portable power sources due to abundant Zn content,low cost and high safety performance.However,owing to the sluggish reaction kinetics of the air cathode,significant battery polarization persists,and a notable disparity remains in key metrics such as rate performance,cycle stability,and energy conversion efficiency compared to industrial requirements.Studies demonstrate that external field-assisted strategies can effectively broaden the reaction interface,accelerate charge transfer,and substantially improve the energy conversion efficiency and cycle life of batteries.At present,in the process of constructing high-performance photo-assisted Zn-air batteries system,it is urgent to solve problems such as insufficient conductivity of the photoelectric cathode,high oxygen adsorption energy barrier,too fast electron-hole recombination rate,low photoelectric conversion efficiency,and easy evaporation of the electrolyte.Therefore,the development of novel photocathode materials with excellent conductive characteristics,high efficiency photogenerated charge separation and multi-field coupling response has become the focus of research.The key lies in maintaining a high carrier separation efficiency and promoting the full contact and reaction between photogenerated electrons and oxygen to achieve rapid oxygen activation and charge transfer.At present,researchers have made significant progress through strategies such as nanostructure regulation and heterostructure construction,but there is still much room for improvement in terms of photoelectric conversion efficiency.In addition,to address the problem of electrolyte evaporation under light illumination,a multi-field coupling-assisted intelligent battery system with an electrolyte circulation function should be developed.By rationally utilizing the external energy field,the continuous separation of photogenerated carriers can be achieved,providing important technical support for constructing an economical and efficient new Zn-air batteries system.Based on the above problems,this thesis mainly focuses on the development of photo-assisted Zn-air cathodes and the rational integration and utilization of external field-assisted strategies,and the following work has been carried out:1.From the perspective of structural design,the utilization of confined spatial structures improves the separation efficiency of photogenerated charge carriers.Inspired by the tunable charge distribution within tubular confined spaces,a one-dimensional confined channel based on molybdenum disulfide（Mo S₂）semiconductor（Mo S₂-ONT）was developed,elucidating the mechanism of rapid photogenerated charge carrier separation and transport within the channel,and developing a high-performance photo-assisted Zn-air battery.Compared with the classic solution strategy of suppressing the rapid recombination of carriers in photocatalysts,the tubular confined space of Mo S₂prepared in this work can achieve more efficient carrier separation and prolong the carrier lifetime.Mo S₂-ONT exhibits a high surface photovoltage,promoting more photogenerated electrons to participate in the reaction and showing excellent photocatalytic effects.Relevant electrochemical tests and theoretical calculation results further indicate that Mo S₂-ONT has faster mass transfer behavior and higher oxygen reduction reaction（ORR）catalytic efficiency.In addition,the Mo S₂-ONT photoelectrode shows excellent energy conversion efficiency,rate performance,and cycle life in photo-assisted Zn-air batteries.This work validates the practicality of the confined carrier separation strategy in photo-assisted Zn-air batteries and provides both a new perspective and key material advancements for the development of next-generation low-cost and high-performance photo-assisted energy storage technologies.2.From the perspective of external field synergy,low-energy fields are utilized to generate piezoelectric effects that promote the continuous separation of photogenerated charge carriers.Inspired by the coupling of optical fields with other external fields to enhance the spontaneous separation and transport dynamics of photogenerated electron-hole pairs,a Zn-air battery that couples optical fields with mechanical fields was developed.This design introduces the piezoelectric effect induced by mechanical fields into the photo-assisted Zn-air battery.The use of a circulating electrolyte mitigates the evaporation under light illumination,and the mechanical force generated by the liquid flow can serve as a pressure source to stimulate the piezoelectric effect.In addition,inspired by the curling property of vine plants in the wind,a micro helical structure piezoelectric photocatalyst withα-Fe₂O₃and poly（vinylidene fluoride-trifluoroethylene）（Fe@P（V-T））was prepared.The periodic deformation of the cathode is caused by the flowing electrolyte,continuously reconstructing the built-in electric field and promoting the continuous separation of carriers.Benefiting from the improvement of the reaction kinetics of the oxygen reduction/oxygen evolution reaction（ORR/OER）by the reconstructed built-in electric field,the charge-discharge overpotential of the photo-assisted Zn-air battery under the condition of micro-vibration generated by the electrolyte circulation is significantly reduced,and the power density is increased by a factor of 3.2.This study offers mechanistic insights into the application of piezoelectric polarization and photo-force coupling strategies in energy storage,while pioneering new avenues for multi-field coupling-assisted Zn-air battery research.3.From the perspective of charge transport channel design,the reaction kinetics of near-neutral Zn-air batteries are regulated using photo-assisted strategies.Inspired by the remarkable effects of photo-assisted strategies in enhancing the reaction kinetics of photoelectric cathodes,a near-neutral Zn-air battery based on photo-responsive molecular sieve materials was developed,with ruthenium-modified titanium silicate molecular sieve（Ru@TS@C）designed as the photocatalyst.The introduction of the photo field into the near-neutral Zn-air battery effectively addresses the sluggish reaction kinetics in a neutral environment.In this study,through spectroscopy tests,photoelectric tests and electronic structure theoretical calculations,the photo-responsive activity of Ru@TS@C was demonstrated,and the photogenerated charge transport mechanism and ORR reaction mechanism in the conductive zeolite were further revealed.The photo-assisted near-neutral Zn-air battery based on Ru@TS@C has obvious 4-electron selectivity and high reversibility,and effectively improves the reaction kinetics of the cathode of the photo-assisted Zn-air battery.The overpotential is only 218 m V at a current density of 0.2 m A cm^-2,which is much lower than 844 m V in the dark condition.This work opens a new research direction for the application of zeolite molecular sieves in photo-assisted Zn-air batteries and provides a theoretical basis and practical guidance for the design and development of high-performance photo-assisted batteries.This dissertation advances the understanding of photo-assisted and multi-field coupled strategies in Zn-air batteries,offering innovative solutions for next-generation energy storage technologies.更多还原