Collaborative Research: Thermodynamics and Ion Transport in Hybrid Organic-Inorganic Block Copolymer Electrolytes

合作研究：杂化有机-无机嵌段共聚物电解质的热力学和离子传输

• 批准号: 1904508
• 负责人: Nitash Balsara
• 金额: $ 25.5万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-07-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904508&HistoricalAwards=false
• 关键词: Collaborative; Research; Thermodynamics; Ion; Transport

NONTECHNICAL DESCRIPTION:Life is increasingly intertwined with electrochemical energy storage, mainly in the form of lithium batteries. They are integral to cellphones, laptops, scooters, electric vehicles, homes, solar installations, and even airplanes. But these basic devices have potential safety hazards because they carry within a highly flammable liquid that has led to explosions and fires. Building an intrinsically safe rechargeable lithium battery remains an unmet challenge, particularly in the development of a nonflammable electrolyte (the material that allows the flow of electrical charge in the battery) to replace the flammable organic liquid electrolyte in current lithium batteries. Polymer electrolytes offer a promising alternative to the flammable liquid. All previous studies have considered polymers made from organic building blocks. The proposed work begins with a novel approach: the synthesis of a hybrid polymer that comprises both organic and inorganic building blocks. The polymer spontaneously forms 10-nanometer-wide alternating organic and inorganic layers (a human hair is 100,000 nanometers wide). This material had very low flammability. The organic layers conduct the lithium ions while the inorganic layers provide mechanical rigidity to the polymer electrolyte, a property that is necessary to keep the two battery electrodes from touching and short-circuiting the battery. The planned work examines the relationship between layer formation and lithium-ion motion through the composite electrolyte. The PIs collaborating on this project will also be working on diversity-related initiatives on the UC Berkeley campus, on organizing public lectures on scientific subjects aimed at high school students in Brooklyn, and on providing multidisciplinary training to undergraduate and graduate students at their institutions.TECHNICAL DESCRIPTION:The proposed work focuses on mixtures of hybrid organic-inorganic block copolymers and a lithium salt. Functionalized polyhedral oligomeric silsesquioxane (POSS) particles are covalently bonded to the inorganic block; the organic block is polyethylene oxide (PEO). The hybrid block copolymers (PEO-POSS) will be synthesized using nitroxide-mediated radical polymerization with functionalized PEO as the macro-initiator. Early results indicate that the phase behavior of pure PEO-POSS block copolymers is as expected: increasing temperature leads to an order-to-disorder transition. In contrast, salt-containing PEO-POSS mixtures exhibit a disorder-to-order transition with increasing temperature. The effect of block ratio, chain length, and POSS functionality will be studied by a combination of depolarized light scattering, X-ray scattering, and electron tomography. Measurements will be made over a wide range of block copolymer compositions, salt concentration, and annealing conditions. The effect of morphology on ion transport will be measured by ac impedance spectroscopy. The intellectual merit of the proposed work will be the study of the thermodynamic interactions and ion transport in an emerging class of hybrid nanostructured polymers comprising fully organic polymers and polymers with covalently-bonded inorganic nanoparticles; the present quantitative understanding of these properties is largely restricted to all-organic chains. .This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

非技术描述：生活越来越多地与电化学能量存储交织在一起，主要是以锂电池的形式交织在一起。 它们是手机，笔记本电脑，踏板车，电动汽车，房屋，太阳装置，甚至飞机的组成部分。 但是这些基本设备具有潜在的安全危害，因为它们在高度易燃的液体中带来了爆炸和火灾。 构建本质上安全的可充电锂电池仍然是一个未满足的挑战，尤其是在开发不易燃式电解质（允许电池中电荷流动的材料）中替代当前锂电池中易燃的有机液体电解质。 聚合物电解质为易燃液体提供了有希望的替代品。 所有以前的研究都考虑了由有机构建块制成的聚合物。 提出的工作始于一种新颖的方法：构成有机和无机构建块的混合聚合物的合成。 聚合物自发形成10纳米范围内的交替有机和无机层（人头发的宽度为100,000纳米）。 该材料的易燃性非常低。有机层进行锂离子，而无机层为聚合物电解质提供机械刚度，这是防止两个电池电极接触和短路电池所必需的特性。 计划的工作检查了通过复合电解质的层形成与锂离子运动之间的关系。在该项目上合作的PI还将致力于在UC Berkeley校园与多样性相关的举措，以组织针对布鲁克林高中生的科学学科的公开讲座，并为他们的机构提供多学科培训，以提供多学科的培训。 盐。 官能化的多面体寡聚硅氧烷（POSS）颗粒与无机块共价键合；有机块是聚乙烯氧化物（PEO）。 将使用氮氧化物介导的自由基聚合以功能化的PEO作为宏观引导剂合成杂化块共聚物（PEO-POSS）。 早期结果表明，纯PEO-POSS块共聚物的相行为是预期的：升高温度会导致订单到订单的过渡。相比之下，含盐的PEO-POSS混合物表现出随温度升高的疾病过渡。 通过去极化光散射，X射线散射和电子断层扫描的结合，将研究块比率，链长和可能功能的影响。 将在各种块共聚物组成，盐浓度和退火条件下进行测量。 形态对离子转运的影响将通过AC阻抗光谱法测量。 拟议工作的智力优点将是对新兴的杂化纳米结构聚合物的热力学相互作用和离子传输的研究，其中包括完全有机聚合物和共价粘结的无机纳米粒子的聚合物；目前对这些特性的定量理解在很大程度上仅限于全有机链。该奖项反映了NSF的法定任务，并通过使用基金会的智力优点和更广泛的影响审查标准来评估值得支持。

项目成果

Comparing Experimental Phase Behavior of Ion-Doped Block Copolymers with Theoretical Predictions Based on Selective Ion Solvation

• DOI: 10.1021/acs.macromol.0c00559
• 发表时间: 2020-05
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Kevin J. Hou;Whitney S. Loo;N. Balsara;Jian Qin

Effect of Added Salt on Disordered Poly(ethylene oxide)- Block -Poly(methyl methacrylate) Copolymer Electrolytes

添加盐对无序聚环氧乙烷-嵌段-聚甲基丙烯酸甲酯共​​聚物电解质的影响

• DOI: 10.1021/acs.macromol.0c02493
• 发表时间: 2021
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Shah, Neel J.;Dadashi-Silab, Sajjad;Galluzzo, Michael D.;Chakraborty, Saheli;Loo, Whitney S.;Matyjaszewski, Krzysztof;Balsara, Nitash P.
• 通讯作者: Balsara, Nitash P.

Propagation of Elliptically Polarized Light through Ordered Block Copolymers

• DOI: 10.1021/acs.macromol.1c01134
• 发表时间: 2021-09-09
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Sharrock, Chappel J.;Cho, Ja Eon;Garetz, Bruce A.
• 通讯作者: Garetz, Bruce A.