Correlations of Li Deficiency, Diffusion, and Interfacial Impedance in Solid-State Batteries Probed by In Situ Tracer Exchange NMR and Depth-Profiling MRI Combined with Modeling

通过原位示踪交换 NMR 和深度剖面 MRI 结合建模探测固态电池中锂缺乏、扩散和界面阻抗的相关性

• 批准号: 1808517
• 负责人: Yan-Yan Hu
• 金额: $ 30.16万
• 依托单位: Florida State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808517&HistoricalAwards=false
• 关键词: Correlations; Li; Deficiency; Diffusion; Interfacial

NON-TECHNICAL SUMMARYAll-solid-state rechargeable batteries promise high energy density, low cost, and improved safety. Therefore, they are considered as the next-generation battery technology for electric vehicles and expected to meet other critical needs for safer, more compact, and higher-capacity energy storage devices. However, low power density and poor long-term stability limit their practical applications and market competitiveness. This research, funded by the Solid State and Materials Chemistry program in the Division of Materials Research at NSF, uses new NMR and MRI techniques to provide new insights into the cause of these limitations and helps to develop high-performance solid-state rechargeable batteries. It also generates new knowledge that promotes in-depth understanding of fundamental interface chemistry, where the bottleneck lies for improved performance of other technologies including fuel cells, super-capacitors, and solar cells. The new NMR and MRI methodologies developed as part of this project not only facilitate the discovery of novel functional materials for technological applications, but might also benefit biomedical research. Additionally, the principle investigator actively recruits students from a HBCU institution and engages women and minority students in the ongoing research, thereby educating and training a diverse next generation of STEM researchers. Outreach activities aimed at engaging the general public in scientific discussions include the development of an app with the title "The Sound of NMR".TECHNICAL SUMMARYLarge resistance for mass and energy transport at electrode-solid electrolyte interfaces impedes the success of high-performance solid-state rechargeable batteries. Understanding Li-ion diffusion across these interfaces and its relationships with structures and compositions of interfaces is critical to addressing the challenges associated with interfacial impedance. This project, funded by the Solid State and Materials Chemistry program in the Division of Materials Research at NSF, probes ion transport through electrode-solid electrolyte interfaces by employing the tracer-exchange NMR method, to quantify Li deficiency with high-resolution depth-profiling magnetic resonance imaging (MRI), and determines interfacial resistance with electrochemical impedance spectroscopy, under both ex and in situ conditions. This study provides insight into the critical factors that limit ion transport at the interfaces, which aids interface design for optimal electrode-electrolyte compatibility with minimized interfacial impedance. The researchers establish real time correlations among Li deficiency, diffusion, and interfacial resistance. Two model systems, Li/Li7La3ZrO12/Li and Li/Li10GeP2S12/Li, are chosen for their representativeness of oxide and sulfide electrolytes and their distinct differences at the Li electrode-solid electrolyte interfaces. Based on the experimental investigation, an analytical model is developed to quantitatively elucidate the impact of Li deficiency and diffusion on interfacial impedance. This model is implemented in the RandFlux software, for predicting the electrochemical processes and performance of all-solid-state rechargeable batteries. For this project, the principle investigator actively recruits students from a HBCU institution and engages women and minority students in the ongoing research. Outreach activities aimed at engaging the general public in scientific discussions include the development of an app with the title "The Sound of NMR".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.

非技术摘要全固态充电电池具有高能量密度、低成本和更高的安全性。因此，它们被认为是电动汽车的下一代电池技术，并有望满足对更安全、更紧凑和更高容量的储能设备的其他关键需求。然而，功率密度低和长期稳定性差限制了其实际应用和市场竞争力。这项研究由 NSF 材料研究部的固态和材料化学项目资助，使用新的 NMR 和 MRI 技术为这些限制的原因提供新的见解，并有助于开发高性能固态可充电电池。它还产生新的知识，促进对基本界面化学的深入理解，而基础界面化学是提高燃料电池、超级电容器和太阳能电池等其他技术性能的瓶颈所在。作为该项目一部分开发的新核磁共振和磁共振成像方法不仅有助于发现用于技术应用的新型功能材料，而且还可能有利于生物医学研究。此外，首席研究员还积极从 HBCU 机构招募学生，并让女性和少数族裔学生参与正在进行的研究，从而教育和培训多样化的下一代 STEM 研究人员。旨在让公众参与科学讨论的外展活动包括开发一款名为“核磁共振之声”的应用程序。 技术摘要电极-固体电解质界面的质量和能量传输阻力较大，阻碍了高性能固态可充电电池的成功。了解锂离子在这些界面上的扩散及其与界面结构和成分的关系对于解决与界面阻抗相关的挑战至关重要。该项目由 NSF 材料研究部的固态和材料化学项目资助，采用示踪剂交换 NMR 方法探测通过电极-固体电解质界面的离子传输，通过高分辨率深度剖析磁共振成像 (MRI) 量化 Li 缺乏，并在外部和原位条件下使用电化学阻抗谱测定界面电阻。这项研究深入了解了限制界面离子传输的关键因素，这有助于界面设计，以最小化界面阻抗实现最佳电极-电解质兼容性。研究人员建立了锂缺乏、扩散和界面电阻之间的实时相关性。选择两个模型系统 Li/Li7La3ZrO12/Li 和 Li/Li10GeP2S12/Li，因为它们具有氧化物和硫化物电解质的代表性以及它们在 Li 电极-固体电解质界面上的明显差异。基于实验研究，开发了一个分析模型来定量阐明锂缺乏和扩散对界面阻抗的影响。该模型在 RandFlux 软件中实现，用于预测全固态充电电池的电化学过程和性能。对于这个项目，首席研究员积极从 HBCU 机构招募学生，并让女性和少数民族学生参与正在进行的研究。旨在让公众参与科学讨论的外展活动包括开发一款名为“核磁共振之声”的应用程序。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力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

High-performance all-solid-state batteries enabled by salt bonding to perovskite in poly(ethylene oxide)

• DOI: 10.1073/pnas.1907507116
• 发表时间: 2019-08
• 期刊: Proceedings of the National Academy of Sciences
• 作者: Henghui Xu;Po‐Hsiu Chien;Jianjian Shi;Yutao Li;Nan Wu;Yuanyue Liu;Yan‐Yan Hu;J. Goodenough

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

• DOI: 10.1002/smtd.202000764
• 发表时间: 2020-09
• 作者: Qiongyu Zhou;Biyi Xu;Po‐Hsiu Chien;Yutao Li;Bing Huang;Nan Wu;Henghui Xu;N. Grundish;Yan‐Yan Hu-Ya

Enhanced Surface Interactions Enable Fast Li + Conduction in Oxide/Polymer Composite Electrolyte

增强的表面相互作用可实现氧化物/聚合物复合电解质中的快速锂传导

• DOI: 10.1002/ange.201914478
• 发表时间: 2020
• 期刊: Angewandte Chemie
• 作者: Wu, Nan;Chien, Po‐Hsiu;Qian, Yumin;Li, Yutao;Xu, Henghui;Grundish, Nicholas S.;Xu, Biyi;Jin, Haibo;Hu, Yan‐Yan;Yu, Guihua
• 通讯作者: Yu, Guihua

Synthesis and characterizations of highly conductive and stable electrolyte Li10P3S12I

• DOI: 10.1016/j.ensm.2019.07.047
• 发表时间: 2019-11-01
• 期刊: ENERGY STORAGE MATERIALS
• 影响因子: 20.4
• 作者: Feng, Xuyong;Chien, Po-Hsiu;Hu, Yan-Yan
• 通讯作者: Hu, Yan-Yan