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: 1904537
• 负责人: Bruce Garetz
• 金额: $ 25.5万
• 依托单位: New York University
• 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 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904537&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。它们是手机、笔记本电脑、踏板车、电动汽车、家庭、太阳能装置甚至飞机不可或缺的一部分。但这些基本设备存在潜在的安全隐患，因为它们内部携带高度易燃的液体，会导致爆炸和火灾。制造一种本质安全的可充电锂电池仍然是一个未解决的挑战，特别是在开发一种不易燃的电解质（允许电池中电荷流动的材料）来取代目前锂电池中易燃的有机液体电解质方面。聚合物电解质是一种很有前途的易燃液体替代品。之前的所有研究都考虑了由有机构建块制成的聚合物。提出的工作以一种新颖的方法开始：合成一种混合聚合物，包括有机和无机构建块。这种聚合物可以自发形成10纳米宽的有机和无机交替层（人的头发有10万纳米宽）。这种材料的可燃性很低。有机层引导锂离子，而无机层为聚合物电解质提供机械刚性，这是防止两个电池电极接触和电池短路所必需的特性。计划中的工作考察了层的形成和锂离子通过复合电解质运动之间的关系。参与该项目的pi还将在加州大学伯克利分校开展与多样性相关的活动，组织针对布鲁克林高中生的科学主题公开讲座，并为其所在机构的本科生和研究生提供多学科培训。技术描述：提出的工作重点是杂化有机-无机嵌段共聚物和锂盐的混合物。功能化多面体低聚硅氧烷（POSS）颗粒与无机嵌段共价结合；有机块是聚氧化物（PEO）。以官能化PEO为宏观引发剂，采用氮氧基自由基聚合法制备了PEO- poss杂化嵌段共聚物。早期结果表明，纯PEO-POSS嵌段共聚物的相行为与预期一致：温度升高导致有序到无序的转变。相比之下，含盐PEO-POSS混合物随着温度的升高呈现出无序到有序的转变。用去偏振光散射、x射线散射和电子断层扫描相结合的方法研究嵌段比、链长和POSS功能的影响。测量将在广泛的嵌段共聚物组成，盐浓度，退火条件。形貌对离子输运的影响将通过交流阻抗光谱来测量。这项工作的智力价值将是研究新兴的混合纳米结构聚合物的热力学相互作用和离子传输，这些聚合物包括全有机聚合物和具有共价键的无机纳米颗粒的聚合物；目前对这些性质的定量认识主要局限于全有机链。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Chimney-Shaped Phase Diagram in a Polymer Blend Electrolyte

聚合物共混电解质中的烟囱形相图

• DOI: 10.1021/acsmacrolett.3c00285
• 发表时间: 2023
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Shah, Neel J.;Shalaby, Marwan;He, Lilin;Wang, Xin;Deslandes, David;Garetz, Bruce A.;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.