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

非技术摘要：这个项目的主要概念来自于人体的神经元回路，作为新型固态电池的范例，基于神经传递的运作机制。大脑通过由神经元网络组成的神经系统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增强的，离子渗透是由跨细胞膜的离子浓度梯度驱动的，离子浓度梯度调节选择性离子通过离子通道。本项目将探索的基于聚合物的固体锂离子电池的概念与神经元网络具有共同的起源，因为它的运作方式是利用拟议的“多层聚合物电解质膜”(MLPEM)上的离子浓度梯度，这些膜在每一层中包含不同的离子浓度，从而产生内部电压。拟议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，即数千个有神经和无神经的细胞膜系列能够产生约600伏的内部电压，以抵御捕食者。就像电动鳗鱼的神经网络允许这种电压再生一样，拟议中的MLPEM电池也可以自行充电。本项目中的自充电电池的工作原理是，移动的锂离子在放电时被输送到正极，而在电池休息时又回到正极，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允许离子浓度梯度的多层聚合物电解质膜来探索这些方面，评估和尝试优化电池的离子导电性、热稳定性和电化学稳定性以及机械性能。如果成功，该项目可能会带来新型的轻质、形状一致、热稳定和电化学稳定、阻燃、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进行跨学科培训和推广活动来整合研究和教育。技术摘要：该项目的灵感来自于身体的神经元电路，作为新型固态电池的范例，基于神经传递的机制，例如由电鳗产生高电压，然后进行内部充电。主要集中在五个方面：(1)开发全固态多层聚合物电解质膜(MLPEM)，使其与电极具有特定的化学和电化学兼容性，以提高储能能力。通过光聚合网络-前体(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)，将具有不同离子密度的单个聚合物电解质(PEM)层堆叠起来，制备MLPEM。因此，在MLPEM中产生的离子浓度梯度将在膜界面上产生电势差，从而提供电池的自我充电能力。(2)在含有增塑剂和改性剂的多元固体电解质中，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的相分离区域，作为建立微电解液电池网络的手段。(3)合成氨基甲酸酯和氨基甲酸酯等PEM添加剂，以防止电极上形成失控的固体电解质界面。(4)将聚乙二醇二胺接枝到多壁碳纳米管(MWCNT)上，然后与氨基甲酸酯类化合物进行封端反应，以改善MLPEM与碳质阳极的界面相容性，同时提高离子电导率。(5)通过锂化聚乙二醇链和/或树枝状聚乙二醇改性MWCNT表面，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。石化树枝状聚乙二醇超支化网络在结构和功能上类似于神经元网络。离子的导电性和迁移率将通过交流阻抗、固态核磁共振和拉曼光谱来确定。电化学稳定性将通过循环伏安法和半电池配置中的恒流充放电循环来评估。利用MLPEM的离子浓度梯度提供的电极之间的自我恢复电位差，电池在静止状态下可以充电，从而延长了电池的寿命。该项目包括通过对学生进行跨学科培训和开展外联活动，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.