浙江理工大学胡毅教授/南京邮电大学赵进教授CEJ：钢筋混凝土结构复合水凝胶电解质的无阴极锌锰纤维电池

Fig.1 Preparation of Zn-Mn fiber batteries. (a) Schematic illustration of the preparation procedure. (b,c) photograph of the fiber batteries with different diameters (b) and the cross-section view (c). (d) Structure illustration of the fiber batteries (inset: cross-section). (e-g) SEM images of the Zn wires coated by PAN (e) and TPU/PAN (f-g) at different preparation stages. (g) is the cross-section of (f). (h) Stress-strain curves of PAM hydrogel with different concentrations of MnSO₄.

本文开发了一种连续制造纤维电池的工艺，以满足现代纺织行业的规模化和效率需求。通过静电纺纱工艺以及简单的紫外引发凝胶前驱体溶液等工艺，在锌线负极表面构建了具有钢筋混凝土结构的复合凝胶电解质，并于导电碳丝复合构建了纤维状无正极水系锌离子电池。本项技术不仅有效提高了生产效率，降低制备成本至每米0.046美元，同时连续化制备的纤维电池可以根据需求制备不同尺寸以及长度，从而适用于多种消费场景。

Fig.2 The influence of PTP on Zn anode. (a) Zn²⁺ transference numbers in different electrolytes. (b) Binding energies of Zn²⁺ ions with H₂O, PAN, TPU, PAM molecules. (c) FTIR spectra (left) and the Zn2p XPS spectra (right). (d) RDF of Zn-O (H₂O) and the radius-dependent coordination numbers. (Inset is the image of PTP system obtained by molecular dynamics). (e) Arrhenius activation energy. (f) CV curves of Zn//stainless steel batteries with different electrolytes at a scanning rate of 1 mV s⁻¹. (g) XRD patterns of the Zn anodes with different systems after 50 cycles at 1 mA cm⁻² and 1 mAh cm⁻³. (h) Adsorption energies of H₂O, PAN, TPU, PAM molecules on Zn anode. (i) Cycling performance of Zn//Zn symmetric button batteries containing different electrolytes. (j) Schematic illustration of the mechanism of PTP composite hydrogel electrolyte in inhibiting HER, accelerating Zn²⁺ transport, and inducing uniform deposition of Zn²⁺.

复合凝胶电解质有效提高了锌负极性能，通过DFT计算，复合凝胶电解质中各组分和锌离子之间的结合能均高于水和锌离子之间的结合能，因此能进一步促进锌离子的脱溶剂化结构，促进锌离子在凝胶电解质中的快速迁移；同时复合凝胶电解质能够促进锌阳极在（002）面的优先吸附，其优异的机械物理性能也能进一步抑制锌枝晶生长。因此复合凝胶电解质相较于传统的水系电解液具有更好的循环稳定性，在1 mA cm⁻²/0.5 mAh cm⁻²条件下，复合凝胶电解质体系下的对称电池稳定运行时间超过2000小时。

Figure 3. Deposition and dissolution of active species on carbon wire cathode. (a) SEM images (left) and Mn mappings (right) of the cross section of carbon wire cathode prepared by constant voltage charging (top) and traditional coating (bottom). (b) Finite element simulation in potential for the carbon wire cathode prepared by constant voltage charging (top) and traditional coating (bottom). (c) SEM images of the carbon wire cathode at different charge and discharge voltages. (d-e) XPS spectra of Mn2p (d) and Mn3s (e) in cathode at different voltages. (f) Schematic illustration of charge/discharge mechanism on carbon wire cathode.

在正极部分，通过恒压充电沉积活性物质，减少工艺流程的同时降低了成本，同时相比于传统涂敷，在具有高孔隙率的纤维电极上使用恒压充电负载活性物质能够渗透入集流体纤维内部，从而提高了MnO_x形成过程中的电子传递效率和高分散；通过在弱酸条件下的碱式硫酸锌（ZSH）辅助沉积/溶解作用，有效提高了容量。

Figure 4. Electrochemical performance of fiber batteries. (a) Schematic illustration of the battery structure with the decoupled hydrogel electrolyte. (b) Cycling performance with different charging time. (c) Rate performance. (d) Coulombic efficiency at different current densities. (e) Cycling performance at different charge voltages. (f) Voltage-energy density curves at different power densities. (g) Ragone plots of the devices in this work compared with recently reported batteries. (h) Comparison of electrochemical performances with previously reported zinc-ion fiber batteries. (i) Long cycle performance of the fiber batteries with decoupled and mixed electrolytes at a charge voltage of 2.2 V for 5 min and a discharge current density of 150 mA cm⁻³.

因此，制备的纤维电池具有优异的倍率性能，同时能够适应一定电压范围下进行充电，以预防在日常生活中的电压波动，纤维电池的容量高达156 mAh cm⁻³，同时能量密度高达227.08 mWh cm⁻³，在2700次循环后能够保持76.5%的容量，经过综合评价，我们的光纤电池在目前报道的锌离子光纤电池中名列前茅。

Figure 5. Adaptability and scalability of fiber batteries. (a) Discharge curves of the fiber batteries under series and parallel conditions. (b) Capacity of the fiber batteries with different lengths. (c) Discharge curves of the fiber batteries with different lengths. (d) Capacity retention of the knotted fiber battery. (e) Capacity retention of the fiber battery immersed in water. (f,g) Photograph of the fiber battery before (f) and after (g) shearing. (h) Photograph of the fiber battery with a length of 5 meters.

纤维电池可以任意进行串并联，同时由于纤维电池独特的一维结构，电池的尺寸可以根据需求裁剪成不同长度，而电池容量也会随着长度的增长而增长，而由于水系锌离子电池的高安全性，被裁剪得每一个部分也能进行单独供电；优秀的机械物理性能以及防水性能能保证纤维电池在任意弯曲条件和水中下进行充放电。

Figure 6. Production and practical application of fabric battery. (a) Schematic illustration of commercial weaving loom. (b) Photograph of the position of fiber batteries in textiles. (c) Photograph of a large-scale fabric battery with spanning 3 meters in length and 0.5 meters in width. (d) Photograph of the fabric batteries powering a mobile phone under folding and heavy pressuring. (e) Soaping test in soapy water with a washing machine and powering a mobile phone after washing. (f) Demonstration of practical application of the fabric battery. (g) Electrocardiography monitored and drawn using the HTS sensor in (f) with a running speed of 25 mm s⁻¹ and a transmission gain of 10 mV mm⁻¹. (h) Environmental data, including temperature, humidity, and vapor pressure deficit, recorded by the HTS sensors in (f) and transmitted to the mobile app by Bluetooth.

凭借纤维电池的种种特性，使用商用织布机将纤维电池和传统纱线进行集成，制备织物电池，织物电池集成了纤维电池优异物理机械性能，能够抵御在日常生活中的外力影响；将织物电池与柔性微型传感器进行集成，构建人体健康检测织物，这些创新的设计代表了可穿戴技术的重大进步，在保持电化学性能和可穿戴性的同时，为能量存储提供了卓越的便利，预示着智能纺织品发展的一个关键里程碑。