Development of multifunctional polymer binders for high performance Si-based anodes of lithium-ion batteries

Zhang, Jiaying

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高性能Si系リチウムイオン電池負極用多機能ポリマーバインダーの開発

https://doi.org/10.18997/0002001053

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sei_k_494.pdf (7.4 MB)

アイテムタイプ

学位論文 = Thesis or Dissertation(1)

公開日

2024-11-21

資源タイプ

資源タイプ識別子

http://purl.org/coar/resource_type/c_db06

資源タイプ

doctoral thesis

タイトル

Development of multifunctional polymer binders for high performance Si-based anodes of lithium-ion batteries

言語

タイトル

高性能Si系リチウムイオン電池負極用多機能ポリマーバインダーの開発

言語

jpn

著者

Zhang, Jiaying

抄録

内容記述タイプ

Abstract

内容記述

Lithium-ion batteries (LIBs) drive the operation of society as the most widely used energy storage device, especially in the fields of mobile devices and electric vehicles (EVs). The demand for the high energy density of the LIBs forces us to develop anode and cathode materials with high specific capacities. The silicon (Si) attracts great attention for its high theoretical specific capacity of 4200 mAh g-1, low lithiation voltage, and plenty of natural resources. However, Si-based electrodes suffer from severe volume expansion and electrode pulverization during cycling, finally causing rapid battery degradation. Many strategies such as Si dimension reduction, morphology control, surface coating, and interface engineering have been proposed to improve the performance of Si anode. Among these, using elaborately designed polymer binders is deemed an efficient tactic to tackle thorny issues. Although binders take a small mass ratio in the electrode preparation (<15%), they can greatly limit the volume expansion and maintain structural instability of the Si electrodes with their specific designed functions, thus improving the electrochemical performance of Si-based LIBs.
In Chapter 1, the overview of LIBs, the development of the Si-based anode materials, the research progress of the polymer binders, and the research purpose of this thesis are introduced. The structure of LIBs and anode/cathode materials are enumerated to give a basic understanding of this research. Then the working mechanism, advantages, and challenges of the Si-based anodes are discussed. Although Si has a high specific capacity, volume expansion (>300%) is the main factor limiting its industrial application. Various methods have been used to improve the electrochemical performance of Si-based anodes, but binder strategies are still one of the favored methods due to their unique role and economically feasible cost. The characteristics of commercially available binders are listed and discussed here, and the design ideas for polymer binders for silicon-based negative electrodes are summarized. Finally, we discuss the research progress of the reported polymer binders and their contributions to the electrochemical performance of Si-based anodes for LIBs.
In Chapter 2, the details of experimental reagents, characterization measurements, the preparation process of Si-based electrodes and cell assembly process, and electrochemical performance measurements are introduced. The purity and manufacturers of chemical reagents are listed, and the models of equipment are indicated. The Si anodes, Si/C anodes, and NCM523 cathodes are prepared according to the detailed description, then they are assembled in the glove box to acquire the half-cells or the full-cells. The essential electrochemical performance, including long-term cycling performance, rate performance, electrochemical impedance spectroscopy, and cyclic voltammetry curves are measured through LAND CT2001A or CHI760 electrochemical workstation.
In Chapter 3, a water-soluble rigid-rod poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT) polymer is described and employed as the binder for Si-based electrodes for the first time. The nematic rigid PBDT bundles wrapped around the Si nanoparticles by hydrogen bonding effectively inhibit the volume expansion of the Si and promote the formation of stable solid electrolyte interfaces (SEI). Moreover, the prelithiated PBDT binder with high ionic conductivity (3.2 × 10−4 S cm−1) not only improves the Li-ions transportation behaviors in the electrode but can also partially compensate for the irreversible Li source consumption during SEI formation. Consequently, the cycling stability and initial coulombic efficiency of the Si-based electrodes with the PBDT binder are remarkably enhanced compared to that with the PVDF binder. This work demonstrates the molecular structure and prelithiation strategy of the polymer binder that plays a crucial role in improving the performance of Si-based electrodes with high-volume expansion.
In Chapter 4, a novel multifunctional polymer binder BDSA–DPA–PEGCE (BDP) incorporated by hard/soft interacting phases was designed. Although the binder design strategy is a key factor for improving the performance of Si anodes of Li-ion batteries, single–function binders may not fulfill their diverse application requirements. The hard domain of the BDP polymer binder is achieved through reversible covalent disulfide exchange, supramolecular noncovalent cooperative H-bonding, and π-π interactions, endowing self-healing ability and enhanced mechanical properties to maintain Si anodes integrity. And the soft phase is dominated by the polyether segment, establishing efficient ion-hopping transportation pathways. Meanwhile, the pre-lithiation strategy is employed for compensating the consumption of Li resources. Volume expansion of Si-based electrodes coordinated by the BDP binder is effectively limited, realizing improved cycling stability, high initial coulombic efficiency of 85.2%, and superior rate performance for Si-based half–cells and NCM523//Si/C full–cell. The BDP binder also promotes the formation of dense, stable, and homogeneous SEI layer.
In general, the cycling stability, initial coulombic efficiency, and rate performance of the Si and Si/C anodes can be improved by the polymer binder’s design. Through polymerization, grafting, cross-linking, pre-lithiation, and other methods, the mechanical properties and ionic conductivity of the polymer binder are effectively improved, thereby optimizing the performance of the Si-based anodes and making it closer to practical applications.This work offers valuable insights for developing advanced polymer binders to satisfy the specific demands of Si-based electrodes for rechargeable batteries, and exploring the field of binders and further improving the performance of Si-based anodes are our goals in the next stage.

内容記述タイプ

TableOfContents

内容記述

1 Introduction| 2 Experimental section| 3 Prelithiated rigid polymer with high ionic conductivity as silicon-based anode binder for lithium-ion batteries| 4 A multifunctional supramolecular polymer binder with hard/soft phase interaction for Si-based lithium-ion batteries

備考

内容記述タイプ

Other

内容記述

九州工業大学博士学位論文学位記番号:生工博甲第494号学位授与年月日:令和6年9月25日

学位授与番号

甲第494号

学位名

博士（工学）

学位授与年月日

2024-09-25

学位授与機関

学位授与機関識別子Scheme

kakenhi

学位授与機関識別子

17104

学位授与機関名

九州工業大学

言語

学位授与年度

内容記述タイプ

Other

内容記述

令和6年度

出版タイプ

VoR

出版タイプResource

http://purl.org/coar/version/c_970fb48d4fbd8a85

アクセス権

open access

アクセス権URI

http://purl.org/coar/access_right/c_abf2

ID登録

10.18997/0002001053

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