【作者】 李明；

【导师】 田明伟；

【作者基本信息】 青岛大学 ， 纺织工程， 2022， 硕士

【摘要】 柔性锌离子电池作为一种便携式高性能移动电源,被广泛应用于可穿戴电子设备和智能纺织品中。然而,目前研究的柔性电池大都基于纸张、薄膜、塑料等柔性基材,无法满足实际应用中的机械形变需求及电子纺织品的一体化设计,且应用模式单一有限。如何制备柔性多功能锌离子电池成为亟待解决的重大问题。纺织纤维材料兼具强度和弹性,疏松多孔的结构特点为活性材料的沉积提供了尽可能大的比表面积,同时缩短离子和电子的传播路径,进一步提高柔性储能器件的电化学性能。此外,纤维基储能设备具有灵活的结构设计以及独特的纺织系统集成能力,被认为是集成到可穿戴能源纺织应用的完美候选者。因此,纤维基锌离子电池的电化学性能研究及功能开发具有实际意义。本项工作采用纺织纤维作为柔性电池基材,分别研究了全纺织基柔性电池、900%超拉伸纤维基柔性电池及连续化耐高温/可漂浮纤维基电池的开发、制备与应用,使纤维基柔性电池在实现自身良好储能性能的同时,可以在弯曲、超拉伸、高温、水中等形变或复杂环境下维持良好的电化学性能。表明纤维基柔性锌离子电池可以适用于多环境、多模式下的供电,显著拓宽了柔性储能设备的应用领域。主要研究工作内容如下:(1)针对普通柔性电池与纺织产品集成困难的问题,提出以纺织纤维为柔性基材,通过针织工艺将柔性电池无缝集成到织物上制成一体化智能纺织品。本研究采用不锈钢/棉复合纤维为柔性基材,利用表面涂覆和电化学沉积的方式成功构筑了二氧化锰/石墨烯改性不锈钢复合纤维基锌锰电池。该全纺织基柔性电池在电流密度为10 mA/cm~3的情况下,比容量可达19.8 m Ah/cm3。此外,它在弯曲形变状态下的电化学性能保持稳定,说明纤维电池在弯曲条件下具有优异的耐久性和电化学稳定性。二氧化锰/石墨烯改性不锈钢复合纤维基锌锰电池良好的可织性、灵活性和柔软性使柔性电子设备的一体化设计成为可能,极大地促进了未来柔性电子器件和智能可穿戴设备的发展。(2)针对普通柔性电池因形变限而导致的破损失灵等问题,提出从结构设计的角度出发,制备了一种具有螺旋结构的900%超拉伸纤维基锌离子电池。预制电池提供了优良的比容量(32.56 m Ah/cm3),能量密度(36.04 m Wh/cm3),以及良好的循环稳定性(76.5%)。集成的可拉伸设备在极端机械变形下具有卓越的超拉伸稳定性,拉伸形变达到900%的状态下仍可保有初始容量的71%。此外,通过编织技术将储能设备集成到纺织品中为LED小灯泡供电,以验证其在可穿戴能源纺织品应用方面的潜力。可以预见,具有螺旋结构的超拉伸集成设备可作为一种强大的弹性电源应用于可拉伸储能设备和可穿戴电子产品。(3)针对目前柔性电池应用模式单一的问题,提出通过自搭建连续化电化学沉积体系和编织技术,实现了一种连续化多功能编织结构锌离子电池的构筑。所制备的连续化锌离子电池具有较高的比容量(30.91 m Ah/cm3)和良好的倍率性能。此外,分别以芳香族聚酰胺纤维及超高分子量聚乙烯纤维为编织纱,利用编织技术制备的耐高温/可漂浮超长纤维基锌离子电池可适用于复杂环境下的警示及救援活动,为柔性储能设备提供了新的应用模式。综上所述,本文探究了以纺织纤维为基材的全纺织基柔性电池、900%超拉伸柔性电池及连续化多功能编织结构锌离子电池,在实现自身良好储能性能的同时,柔性电池可以在弯曲、超拉伸、扭转、高温、水中等形变或复杂环境下维持良好的电化学性能,表明纤维基柔性锌离子电池可以适用于多环境、多模式下的供电,显著拓宽了柔性储能设备的应用领域。更多还原

【Abstract】 As a portable high-performance energy storage,flexible Zn-ion battery is widely used in wearable electronics and smart textiles.However,the reported flexible batteries are mostly based on flexible substrates such as paper,film and plastic with limited function,which cannot satisfied the mechanical deformation and all-in-one design in practical application.Therefore,the key challenge lies on how to fabricate a multifunctional fiber-based battery.Textile fibers possess strength and elasticity.The porous structure provides as large specific surface area as possible for the deposition of active materials,which shorten the transport path of ions and electrons and further improves the electrochemical performance of flexible energy storage devices.Furthermore,fiber-based energy storage devices have been regarded as perfect candidates for integration into wearable energy textile applications,owing to their flexible structural design and unique capacity for integration with textile systems.Therefore,it is essential to discuss the electrochemical performance and functional exploitation of fiber-based Zn-ion battery.In this paper,the exploitation,fabrication and application of the whole textile-based flexible Zn-ion battery,900%ultrastretching fiber-based Zn-ion battery and multi-functional braided Zn-ion battery are studied.The flexible battery can not only realize excellent electrochemical performance,but also exhibit superior stability under deformation or complex environment,such as bending,ultra-stretching,high temperature or in water.The results show that the flexible Zn-ion battery could power in multi-environment and multi-mode,which significantly broadens the application of flexible energy storage devices.The main research contents of this paper are as follows,（1）In view of the intricate integration of flexible battery and textiles,all-in-one smart textile are fabricated with fiber-based Zn-ion battery through facile knitting technology.In this study,Mn O₂/graphene modified stainless steel composite fiber-based Zn-ion battery is successfully fabricated by coating and electrochemical deposition.The fiber-based flexible battery possess a high specific capacity of 19.8m Ah/cm³ at a current density of 10m A/cm³.In addition,it exhibits stable electrochemical performance under bending,suggesting excellent durability under deformation.The excellent weavability,flexibility and flexibility of Mn O₂/graphene modified stainless steel composite fiber-based Zn-ion battery make it possible to construct the"all-in-one"flexible electronic devices,which greatly promotes the development of flexible electronic devices and intelligent wearable devices in the future.（2）In view of the breakage and failure caused by limited deformation of common fiber battery,a novel 900%ultrastretchable fiber-based Zn-ion battery with a helix structure is designed,inspired by the unique natural“structure-designable”case of luffa tendrils.The prefabricated battery delivers an enhanced specific capacity（32.56m Ah/cm³）,superior energy density（36.04m Wh/cm³）and an excellent cycling stability（76.5%capacity remained after 1000 cycles）.The integrated stretchable device presents superior ultrastretchable stability under extreme mechanical deformation,and it could maintain 71%of its original capacity after stretching to the 900%limit.In addition,the integrated devices are knitted into textiles to power LEDs for the validation of their potential for wearable energy textile applications.We foresee that an ultrastretchable integrated device with a helix structure is essential for the structural design of stretchable energy storage devices and wearable electronics.（3）In view of the limited application of flexible battery,a continuous multi-functional braided Zn-ion battery is constructed with home-made continuous electrochemical deposition equipment and braided technology.The prepared continuous Zn-ion battery possesses high specific capacity（30.91m Ah/cm³）and excellent rate performance.Furthermore,continues heat-resistant/floated braided Zn-ion batteries are fabricated with aromatic polyamide fiber and UHMWPEF used as braided yarns.The continuous multi-functional braided Zn-ion battery is suitable for warning and rescue activities in complex environment,providing a new application mode for flexible energy storage equipment.Generally speaking,the whole textile-based flexible Zn-ion battery,900%ultrastretching fiber-based Zn-ion battery and multifunctional braided Zn-ion battery are studied in this paper.While achieving well energy storage performance,the flexible fiber-based battery could maintain excellent electrochemical performance under bending,stretching,twisting,high temperature,in water and other deformation or complex environment.The results indict that the flexible fiber-based Zn-ion battery is suitable for multi-environment and multi-mode,which significantly broadens the application field of flexible energy storage devices.更多还原