Neurotechnologically inspired multilayered polymer electrolyte membranes to harness ion concentration gradient for energy restoration

非技术概述：该项目的主要概念来自于身体的神经元回路，作为基于神经传递机制的新型固态电池的范例。大脑通过由神经网络组成的神经系统来控制身体的各种功能。神经元是可兴奋的，单个细胞与周围的其他神经元进行特定的接触。它们的信号处理是由离子渗透驱动的，离子渗透是由细胞膜上的离子浓度梯度驱动的，离子浓度梯度调节了选择性离子通过离子通道的通道。该项目探索的基于聚合物的固体锂离子电池的概念与神经网络有着共同的起源，因为它通过利用拟议的“多层聚合物电解质膜”（MLPEM）上的离子浓度梯度来运行，每层中含有不同的离子浓度，从而产生内部电压。提出的浓度梯度电池设计方法在概念上类似于电鳗的神经元操作，即由数千个受神经支配和非神经支配的细胞膜组成的系列能够产生约600伏的内部电压来抵御捕食者。就像电鳗的神经网络允许这种电压再生一样，提议的MLPEM电池可以自己充电。本项目自充电电池的工作原理是，在放电时，移动的锂离子会被输送到阴极，但在电池休息时，它会回到阳极，从而恢复离子浓度梯度，从而恢复电压。本项目将通过合成和加工多层聚合物电解质膜来探索这些方面，允许离子浓度梯度，评估并尝试优化离子电导率，热学和电化学稳定性以及电池的机械性能。如果成功，该项目可能会带来新型轻质、形状符合要求、热稳定性和电化学稳定性、阻燃性和可自我充电的电池，从而造福社会。该项目还包括通过对学生的跨学科培训和外联活动将研究和教育结合起来。技术概述：该项目的灵感来自于身体的神经元回路，作为基于神经传递机制的新型固态电池的范例，例如电鳗产生高压，然后进行内部充电。该研究主要集中在五个重点领域：(1)开发与电极具有特定化学和电化学相容性的全固态多层聚合物电解质膜（MLPEM），以提高储能能力。MLPEM将通过光聚合网络-前驱体（聚乙二醇二丙烯酸酯）/固体增塑剂（丁二腈）/离子盐（双三氟磺酰亚胺锂）叠加具有不同离子居群的单个聚合物电解质（PEM）层来制备。因此，在MLPEM中产生的离子浓度梯度将在膜界面上产生电位差，从而提供电池的自充电性。(2)在含有增塑剂和改性剂的多组分固体电解质中，通过全息光聚合诱导相分离，制备具有不同浓度梯度的定向排列相分离畴，作为创建微电解质电池网络的一种手段。(3)合成氨基羰基氨基甲酸酯、氨基氨基甲酸酯等PEM添加剂，防止电极上不受控制的固体电解质界面形成。(4)将聚乙二醇二胺接枝到多壁碳纳米管（MWCNT）上，并与氨基甲酸酯衍生物端盖反应，提高MLPEM与碳质阳极的界面相容性，同时提高离子电导率。(5)通过接枝锂化PEG链和/或枝状PEG对MWCNT表面进行修饰，以提高锂离子的存储容量，并为电子和离子的传导提供单独的途径。在结构和功能上，锂化的乔木型超支化聚乙二醇网络类似于神经网络。离子电导率和迁移率将由交流阻抗、固态核磁共振和拉曼光谱测定。电化学稳定性将通过循环伏安法和半电池结构的恒流充放电循环来评估。利用MLPEM离子浓度梯度提供的电极间自恢复电位差，使电池在静息状态下可充电，从而延长电池寿命。该项目包括通过对学生的跨学科培训和外联活动将研究和教育结合起来。

NON-TECHNICAL SUMMARY:The main concept of this project emerges from the neuronal circuits of the body as paradigms for novel types of solid-state batteries based on mechanisms operative in neurotransmission. The brain controls various functions of the body through the nervous system composed of neuronal networks. Neurons are excitable, individual cells making specific contacts with other surrounding neurons. Their signal-processing is empowered by ion osmosis, driven by ion concentration gradients across the cell membrane which regulates passage of selective ions via ionic channels. The concept of polymer-based solid lithium ion batteries to be explored in this project shares this common origin with neuronal networks, as it operates by harnessing ion concentration gradients across the proposed "multilayered polymer electrolyte membranes" (MLPEM) which contain different ion concentrations in each layer, thus generating an internal voltage. The proposed concentration-gradient approach to battery design is conceptually similar to the neuronal operation of an electric eel, whereby series of thousands of innervated and non-innervated cell membranes are capable of generating internal voltages of about 600 volts to fend off predators. Just as the neural network of the electric eel allows this voltage to be regenerated, the proposed MLPEM batteries could be rechargeable on their own. The working principle of the self-rechargeable battery in this project is that the mobile lithium cation will be transported to the cathode during discharging, but it will revert back to the anode during battery resting, thereby restoring the ion concentration gradient and hence a voltage. This project will explore these aspects by synthesizing and processing multilayered polymer electrolyte membranes allowing ionic concentration gradients, evaluate and attempt to optimize the ionic conductivity, the thermal and electrochemical stability, and the mechanical properties of the battery. If successful, this project may benefit society by leading to novel lightweight, shape-conformable, thermally and electrochemically stable, flame-retardant, self-rechargeable batteries. The project also includes integration of research and education through interdisciplinary training of students and outreach activities.TECHNICAL SUMMARY:This project is inspired by the neuronal circuits of the body as paradigms for novel types of solid-state batteries based on mechanisms operative in neurotransmission, e.g. the generation of high voltages by electric eels followed by internal recharging. It focuses on five thrust areas: (1) Development of all-solid-state multilayered polymer electrolyte membranes (MLPEM) having specific chemical and electrochemical compatibility with electrodes for enhancing energy-storage capacity. MLPEM will be fabricated by stacking individual polymer electrolyte (PEM) layers having different ion populations by photopolymerizing network-precursor (poly(ethylene glycol) diacrylate)/solid plasticizer (succinonitrile)/ionic salt (lithium bis-trifluorosulfonylimide). The ion concentration gradient thus produced in MLPEM will create potential differences across the membrane interfaces, thereby affording self-rechargeability of the battery. (2) Fabrication of directionally aligned phase-separated domains having various concentration gradients via holographic photopolymerization-induced phase separation in multicomponent solid electrolytes containing plasticizer and modifiers as a means of creating networks of micro-electrolyte cells. (3) Synthesis of PEM additives such as amido-carbonyl carbamate and amido-carbamate to prevent uncontrolled solid electrolyte interface formation on electrodes. (4) Grafting of poly(ethylene glycol) diamine to multiwall carbon nanotube (MWCNT) followed by end-capped reaction with carbamate derivatives to improve interface compatibility of MLPEM with carbonaceous anode and concurrently increase in ionic conductivity. (5) Modification of MWCNT surface by grafting of lithiated PEG-chains and/or arborescent PEG to raise lithium ion storage capacity and provide separate pathways for electron and ion conductions. The network of lithiated arborescent hyperbranched PEG resembles a neuronal network structurally and functionally. The ion conductivity and mobility will be determined by AC impedance, solid-state NMR, and Raman spectroscopy. Electrochemical stability will be evaluated by means of cyclic voltammetry and galvanostatic charge/discharge cycling in half-cell configurations. By virtue of the self-restored potential difference between the electrodes afforded by the ion concentration gradient of MLPEM, the battery would be rechargeable in the rest state, thereby prolonging the battery life. The project includes integration of research and education through interdisciplinary training of students and outreach activities.