固态锂金属电池开发及电极界面对电化学性能影响的机理研究

目前锂离子电池（LIBs）具有十分广泛的应用前景，但是能量密度受限、枝晶生长和安全隐患较大等缺点限制了LIBs的进一步发展。为了解决以上问题，有研究提出通过研发固态电解质（SSEs），减少或杜绝使用易燃易爆成分，装配使用锂金属作为电极的固态锂金属电池（SSLMBs）从而提升电池的能量密度和安全性。但是同样存在一些问题阻碍了SSLMBs的实际应用，例如SSEs刚性结构导致机械性能较差离子电导率较低；此外由于SSEs和电极之间的界面主要为点接触导致界面湿润性差；SSEs的刚性结构并不能完全抑制锂枝晶在电解质内部的生长，甚至在某些情况还会促进其生长；最后是SSLMBs中对其界面微观结构的研究较为缺乏，例如固体电解质界面（SEI）组分和结构对电池电化学性能的影响机理尚不明确。

本课题提出了一种基于聚偏氟乙烯-六氟丙烯共聚物（PVDF-HFP）基体的聚合物固态电解质（PPE），通过使用碳酸丙烯酯作为塑化剂，有效提高了PPE的界面湿润性并使其离子电导率室温下达到1.15×10^-3 S cm^-1。此外，还研究了使用不同锂盐提供自由穿梭的离子和不同塑化剂作为添加剂时对电池电化学性能的影响。当PPE体系组分包含LiBF₄与碳酸丙烯酯时，对称电池循环时间超过1000 h。通过低剂量冷冻透射电子显微镜（Cryo-TEM）表征，揭示了Li负极与PPE之间的高界面相容性。SSLMBs的SEI由可以与PPE保持紧密接触的无定形外层，以及Li₂O主导的内层组成，该内层可以避免Li在电池循环过程中发生连续的副反应。根据表征结果提出了在靠近Li负极的PPE区域存在富含LiF的过渡层。本课题证明了Cryo-TEM技术在研究聚合物基固态电池中界面相的优势，该技术将来可以广泛用于从SSEs微观界面结构合理化解释其与电池性能之间的关联。

At present, lithium-ion batteries (LIBs) have very wide application prospects, but the drawbacks of limited energy density, dendrite growth, and high safety hazards limit the further development of LIBs. To address these issues, researchers have proposed to develop solid-state electrolytes (SSEs) to reduce or eliminate the use of flammable and explosive components, and to assemble solid-state lithium metal batteries (SSLMBs) with lithium metal as the electrode, thereby improving the energy density and safety of the batteries. However, there are several issues that hinder the practical application of SSLMBs. For example, the rigid structure of SSEs leads to poor mechanical performance and low ionic conductivity. In addition, the interfaces between SSEs and electrodes are mainly point contacts, resulting in poor interface wettability. The rigid structure of SSEs cannot completely suppress the growth of lithium dendrites in the electrolyte, and in some cases may even promote their growth. Finally, there is a lack of research on the microstructure of the interphases in SSLMBs. For example, the mechanism by which the composition and structure of the solid electrolyte interphase (SEI) affect the electrochemical performance of the battery is still unclear.

Herein, this project develops a novel Poly Vinylidenefluoride-hexafluoro Propylene (PVDF-HFP)-based polymer electrolyte (PPE) with propylene carbonate as the plasticizer. It effectively improved the interfacial wettability and achieved an ionic conductivity of 1.15×10^-3 S cm^-1 at room temperature for the PPE. In addition, the effects of using different lithium salts provide free-shuttle ions and different plasticizers as additives on the electrochemical performance of the battery are also investigated. When the PPE system components include LiBF₄ and propylene carbonate, the symmetrical cell can operate for over 1000 h. Low-dose cryogenic transmission electron microscopy (Cryo-TEM) characterization reveals the high interfacial compatibility between Li metal anode and PPE. The SEI of SSLMBs is made up of an amorphous outer layer, which can keep intimate contact with PPE, and a Li₂O-dominated inner layer, which can protect Li from continuous side reactions during battery cycling. According to the characterization results, a LiF-rich transition layer is also discovered in the region of PPE close to the Li metal anode. This project demonstrates the feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques, which could be widely employed in the future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.

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