随着环境污染和能源危机等世界性问题的日益突出，人类对寻找绿色、可持续、环境友好型能源的需求与日俱增，这明确了人们对新能源领域探索的目标，同时，也加快了科学家们开发对各种能量收集技术的步伐。在多样的能量收集技术中，摩擦纳米发电机（TENG）作为一种清洁、环保、高效的能量收集设备，能够从周围环境中收集能量，如风能、海洋能、机械振动以及人体运动等。TENG集重量轻、成本低、转换效率高、输出电性能高等优点于一身，因此，吸引了科学家们的广泛关注。TENG能充分利用人体运动所产生的机械能，通过摩擦起电和静电感应的耦合作用将机械能转化成电能。TENG主要由正、负摩擦层两个关键部分组成，摩擦层在运行的过程中产生相反的电荷，从而在决定输出电性能起着至关重要的作用。选择具有特殊材料和独特结构的摩擦层对实现高输出电性能的TENG具有关键性作用。此外，由生物相容性和生物可降解性的材料组成的摩擦层不仅适合回收循环利用，还能应用到生物医学领域中，为自供电生物电子设备的发展提供了广泛的应用前景。

      本论文通过结合丝素蛋白、MXene、聚二甲基硅氧烷（PDMS）、气凝胶、海绵等结构材料的各自优点，制备了一系列生物材料基摩擦纳米发电机及柔性传感器，不仅解决了生物材料基TENG输出电性能低的问题，还赋予其多功能一体化的特点。此外，本论文通过该生物材料基TENG还设计出摩擦电眼罩、口罩等自供电电子器件，为实时监测人体运动、睡眠、呼吸状态以及诊断失眠、哮喘症状等相关疾病提供了潜在的应用价值。本文主要开展了以下研究：

   （1）针对生物材料基摩擦纳米发电机输出电性能低这一难题，可通过增大摩擦层材料的有效接触面积来增加摩擦纳米发电机的输出电性能。本论文设计了丝素蛋白薄膜基摩擦纳米发电机和丝素蛋白气凝胶基摩擦纳米发电机。通过分析丝素蛋白薄膜基TENG和丝素蛋白气凝胶基TENG的工作原理，实验结果表明，与丝素蛋白薄膜基TENG相比，丝素蛋白气凝胶基TENG的输出电性能显著提高。其中，输出电压和电流分别提高了6.5倍和4.5倍。为了进一步优化丝素蛋白气凝胶基TENG的输出电性能，我们还系统地研究了丝素蛋白浓度、操作压强、接触面积、工作频率、工作温度、器件的弯曲角度等因素对TENG输出电性能的影响，得到了输出电压、电流以及功率密度的最大值，分别为365V、11.8μA和7.52W/m²。值得注意的是，这是目前研究报道中纯丝素蛋白气凝胶基TENG功率密度的最大值。同时，成功地解决了生物材料基TENG输出电性能低的难题。此外，由于丝素蛋白气凝胶具有良好的生物相容性、机械稳定性等优点，我们还开发了一种丝素蛋白气凝胶基TENG自供电传感器，用于收集人体生物力学所产生的能量，为自供电可穿戴电子领域开发低成本、高输出电性能的生物材料基TENG提供了一种有效的方法。

    （2）采用材料表面改性的方法，提高摩擦层材料的电荷密度，进而增加TENG的输出电性能。本论文结合丝素蛋白、MXene的优点，设计了一种高性能丝素蛋白-MXene复合薄膜基TENG。在丝素蛋白薄膜中引入MXene增加了其表面电荷密度，通过调节MXene在复合薄膜中的比例（MXene含量为40%），丝素蛋白-MXene复合薄膜基TENG达到了最佳的输出电性能，最大开路电压为418V，最大短路电流为11.6μA，最大输出功率为9.92W/m²。与之前报道的丝素蛋白薄膜基TENG的输出性能最大值相比，我们的丝素蛋白-MXene复合薄膜基TENG的电压和功率密度提高了1.6倍和3.8倍。为了进一步优化其输出电性能，我们还系统的研究了不同电极、压强和频率对输出电性能的影响，确定了最佳的工作条件。此外，由于丝素蛋白-MXene复合薄膜具有良好的生物相容性和优异的遮光性，我们还设计了一种智能丝素蛋白-MXene复合薄膜基摩擦电眼罩，它能明显诊断失眠症状的信号，并用于实时监测睡眠质量，为可穿戴电子设备诊断失眠症状及相关性疾病提供了潜在的应用价值。

    （3）基于前两章工作的研究基础，我们同时运用提高摩擦层的有效接触面积与材料表面改性两种方法，提升摩擦纳米发电机的输出电性能效果非常显著。本论文结合丝素蛋白、MXene、PDMS、气凝胶和海绵的生物相容性、高孔隙率、高比表面积等诸多优点，设计出一种具有高能源转换效率、超高输出电性能的丝素蛋白@MXene复合气凝胶基TENG。该TENG的正、负摩擦层材料分别为丝素蛋白@MXene复合气凝胶和PDMS海绵。在丝素蛋白气凝胶中引入MXene，不仅增加了复合气凝胶的比表面积，还明显增加了其表面电荷密度。通过调节丝素蛋白与MXene的比例, 丝素蛋白@MXene复合气凝胶基（丝素蛋白:MXene = 1:1）TENG实现了最佳输出电性能，电压、电流和功率密度分别为545V、16.13μA和13.25W/m²。与我们最初的丝素蛋白-PDMS薄膜基TENG输出电性能（电压：56V，电流：2.6μA）相比，其电压和电流分别提高了约10倍和6倍，同时，与之前报道的气凝胶基TENG功率密度最大值相比，我们报道的TENG功率密度提高了约2-3倍。此外，由于丝素蛋白@MXene复合气凝胶具有公认的生物相容性和优异的透气性，我们开发了一种丝素蛋白@MXene复合气凝胶基摩擦电口罩，它能有效的诊断哮喘症状迹象，并实时监测人体呼吸状态，为自供电生物电子设备诊断哮喘症状及相关的呼吸系统疾病提供了广泛的应用前景。

    （4）上述三章工作主要讨论了以丝素蛋白为正摩擦层材料的设计与性能优化。最后，本论文重点研究了负摩擦层PDMS的应用。以糖为模板制备了PDMS海绵，将AgNWs负载到PDMS海绵中，再涂上一层PDMS薄膜，制备出具有三维多孔结构的PAP海绵。通过上述研究，本论文成功设计出一种柔性多孔的、高灵敏度的PAP海绵基电容式压力传感器。通过详细地研究糖模板的比例、AgNWs的负载量对PAP海绵基传感器传感性能的影响，我们发现当以100%纯蔗糖为模板，AgNWs的负载量为150mg时，PAP海绵基压力传感器展示出最优的电容响应能力，其灵敏度高达0.62 kPa⁻¹。通过对优化的PAP海绵进行表征，结果显示PAP海绵具有优异的机械性能，其中伸长率为156.38%，抗拉强度高达1.425MPa。此外，该传感器还兼具优异的防水性能、高弹性、低迟滞性、质轻等诸多优点，为开发出低成本、高能源转换率、高灵敏度的环境友好型柔性传感器设备提供了一种可行的途径。

         With the increasing prominence of global issues such as environmental pollution and energy crisis, there is growing need to find green, sustainable and environmentally friendly energy sources, which has clarified the goal of exploring the new energy field and accelerated the pace of scientists in developing a variety of energy harvesting technologies. Among the various energy harvesting technologies, triboelectric nanogenerator (TENG), as a clean, environmentally friendly, and efficient energy harvesting devices, can harvest energy from the surrounding environment, such as wind energy, ocean energy, mechanical vibration, and human movement, etc. TENG combines the advantages of lightweight, low cost, high conversion efficiency and high output electrical performance, and therefore attracts a lot of attention from scientists. TENG can fully utilize the mechanical energy generated by human movement, and convert mechanical energy into electrical energy through friction electrification and electrostatic induction coupling. TENG is mainly composed of two key parts, the positive and negative triboelectric layers, which generate opposite charges during operation, and thus plays a crucial role in determining the output electrical performance. The selection of triboelectric layers with special materials and unique structures plays a key role in realizing high output electrical performance of TENG. In addition, triboelectric layers composed of biocompatible and biodegradable materials are not only suitable for recovery and recycling, but can also be used in biomedical applications, which provide a wide range of application prospects for the development of self-powered bio-electronic devices.

          In this dissertation, a series of biomaterial-based triboelectric nanogenerators and flexible sensors are prepared by combining the respective advantages of structural materials such as silk fibroin, MXene, polydimethylsiloxane (PDMS), aerogel, sponge, etc., which not only solve the problem of the low output electrical performance of the biomaterial-based TENG, but also endows it with multifunctional integration features. In addition, this project also designs self-powered electronic devices such as triboelectric eye masks and masks through this biomaterial-based TENG, which provides potential applications for real-time monitoring of human movement, sleep and respiratory status, as well as diagnosis of insomnia, asthma symptoms and other related diseases. In this paper, the following studies are carried out:

        (1) To address the challenge of low output electrical performance of biomaterial-based triboelectric nanogenerators, the output electrical performance of triboelectric nanogenerators can be improved by increasing the effective contact area of the triboelectric layer material. In this project, the silk fibroin film-based triboelectric nanogenerator and silk fibroin aerogel-based triboelectric nanogenerator are designed. By analyzing the working principles of silk fibroin film-based TENG and silk fibroin aerogel-based TENG, the experimental results show that the output electrical performance of silk fibroin aerogel-based TENG is significantly improved compared with silk fibroin film-based TENG. Among them, the output voltage and current were increased by 6.5 and 4.5 times, respectively. In order to further optimize the output electrical performance of silk fibroin aerogel-based TENG, we also systematically investigated the effects of silk fibroin concentration, operating pressure, contact area, operating frequency, operating temperature, and bending angle of the device on the output electrical performance of the TENG. We achieved the maximum values of the output voltage, current, and power density, which were 365V, 11.8μA, and 7.52W/m², respectively. Notably, this is the maximum value of power density of pure silk fibroin aerogel-based TENG reported in the current study reports. Meanwhile, we successfully solved the challenge of low output electrical performance of biomaterial-based TENG. In addition, due to the advantages of silk fibroin aerogel such as good biocompatibility and mechanical stability, we have developed a self-powered silk fibroin aerogel-based TENG sensor for harvesting the energy generated by human biomechanics, which provides an effective method for developing low-cost biomaterial-based TENG with high output electrical performance in the field of self-powered wearable electronics.

        (2) We use the method of material surface modification to increase the charge density of triboelectric layer materials and thus increase the output electrical performance of TENG. In this project, a high-performance silk fibroin-MXene composite film-based TENG was invented by combining the advantages of silk fibroin and MXene. The introduction of MXene into the silk fibroin film increased its surface charge density, and by adjusting the proportion of MXene in the composite film (the MXene content was 40%), the silk fibroin-MXene composite film-based TENG reached the optimal output electrical performance. The maximum open-circuit voltage was 418V. The maximum short-circuit current was 11.6μA. The maximum output power was 9.92W/m². Compared with the maximum output performance of silk fibroin film-based TENG reported previously, our silk fibroin-MXene composite film-based TENG showed an increase in the voltage and power density by 1.6 times and 3.8 times. In order to further optimize its output electrical performance, we also systematically investigated the effects of different electrodes, pressures, and frequencies on the output electrical performance to determine the optimal operating conditions. In addition, due to the good biocompatibility and excellent light-shielding properties of the silk fibroin -MXene composite film, we designed a smart silk fibroin-MXene composite film-based triboelectric eye mask. It can obviously diagnose the signals of insomnia symptoms and apply to real-time monitoring of the quality of sleep, which provides a potential application for wearable electronic devices to diagnose insomnia symptoms and related diseases.

       (3) Based on the research basis of the work in the previous two chapters, we simultaneously applied both methods of increasing the effective contact area of the triboelectric layer and material surface modification to enhance the output electrical performance of the triboelectric nanogenerator with very significant results. In this project, we designed a silk fibroin @MXene composite aerogel-based TENG with high-energy conversion efficiency and ultra-high output electrical performance by combining the biocompatibility, high porosity, high specific surface area, and many other advantages of silk fibroin, MXene, PDMS, aerogel, and sponge, etc. The positive and negative triboelectric layer materials of the TENG were silk fibroin@MXene composite aerogel and PDMS sponge. The introduction of MXene into the silk fibroin aerogel not only increased the specific surface area of the composite aerogel, but also significantly increased its surface charge density. By adjusting the ratio of silk fibroin to MXene, the silk fibroin @MXene composite aerogel-based (silk fibroin:MXene = 1:1) TENG achieved the optimal output electrical performance with voltage, current, and power density of 545V, 16.13μA, and 13.25W/m², respectively. Compared with our initial silk fibroin-PDMS film-based TENG output electrical performance (voltage: 56V, current: 2.6μA), the voltage and current have been improved by about 10 times and 6 times, respectively, while the power density of our reported TENG has been improved by about 2-3 times compared with the maximum power density of aerogel-based TENG reported previously. In addition, due to the recognized biocompatibility and excellent breathability of silk fibroin@MXene composite aerogel, we invented an silk fibroin@MXene composite aerogel-based triboelectric mask. It can effectively diagnose the signs of asthma symptoms and monitor the respiratory status of the human body in real time, providing a wide range of applications for self-powered bioelectronic devices to diagnose asthma symptoms and related respiratory system diseases.

        (4) The first three chapters of the above work focus on the design and performance optimization of the material with silk fibroin as the positive triboelectric layer. Finally, this project focuses on the application of PDMS as the negative triboelectric layer. PDMS sponges were prepared by using sugar as a template, loading AgNWs into PDMS sponges, and then coating a PDMS film to prepare PAP sponges with a three-dimensional porous structure. Through the above studies, this project successfully designed a flexible and porous PAP sponge-based capacitive pressure sensor with high sensitivity. By studying the effects of the ratio of sugar template and the loading amount of AgNWs on the sensing performance of the PAP sponge-based sensor, we found that the PAP sponge-based pressure sensor demonstrated the optimal capacitive response capability. Its sensitivity was as high as 0.62 kPa⁻¹ when 100% pure sucrose was used as the template and the loading amount of AgNWs was 150 mg. Through the characterization of the optimized PAP sponge, the results show that the PAP sponge has excellent mechanical performance, including an elongation of 156.38% and a tensile strength of up to 1.425 MPa. In addition, the sensor also has excellent waterproof performance, high elasticity, low hysteresis, lightweight and many other advantages, which provides a feasible way to develop environmentally friendly flexible sensor devices with low cost, high-energy conversion rate and high sensitivity.