Development of novel materials for next-generation battery ecosystems

국문 초록 (Abstract)

최근 전 세계적으로 전기 자동차의 급속한 보급으로 심각한 환경 문제가 대두되고 있으며, 특히 수명 종료 전략과 전자 폐기물 위기가 심각해지고 있습니다. 이러한 과제를 해결하기 위해 현재 연구는 정밀한 비용 및 환경 요건을 충족하는 고성능 소재 설계를 목표로 하는 기술 발전을 우선시하고 있습니다.
본 학위논문은 두 가지 주요 목표를 기술합니다. 첫째, 전기차 배터리의 순환 경제에 대한 시급한 요구에 대응하여, 사용후 리튬이온 배터리에서 니켈과 리튬을 추출하는 새로운 추출제를 개발하였습니다. 계산적 접근을 통해 추출제의 합리적 설계를 유도했으며, 공정 집약화 및 효율적인 용매 추출을 위해 연속흐름반응 시스템을 도입했습니다. 이 전략은 높은 선택성을 확보하는 동시에, 습식제련 공정의 핵심 난제인 황산나트륨을 획기적으로 저감하는 최적의 추출제를 개발하는 성과로 이어졌습니다. 둘째, 다용도 설포닐 플루오라이드 기반 소재 플랫폼을 합성하였습니다. 이 신규 소재는 리튬이온 배터리의 고성능 전해질 첨가제이자 DNA-Encoded Libraries (DELs)의 기능성 골격으로 활용될 수 있는 이중 응용의 높은 잠재력을 입증합니다.

다국어 초록 (Multilingual Abstract)

Recently, the rapid global adoption of electric vehicles (EVs) has given rise to significant environmental hurdles, particularly concerning end-of-life strategies and the emerging crisis of electronic waste. To address these challenges, current research is prioritizing technological advancements aimed at designing high-performance materials that meet precise cost and environmental requirements.
In this dissertation, two primary objectives are described. First, addressing the critical need for a circular economy for electric vehicle (EV) batteries, novel extractants for nickel and lithium from spent Lithium-Ion batteries (LiBs) were developed. The computational approach guided the rational design of extractants, while an Advanced Flow Reactor (AFR) system was employed for process intensification and efficient solvent extraction. This strategy resulted in an optimal extractant that not only shows high selectivity but also enables significant sodium sulfate (Na2SO4) reduction, a key challenge in hydrometallurgical processing. Second, a versatile sulfonyl fluoride-based material platform was synthesized. This novel material demonstrates significant potential for dual-use applications such as high-performance electrolyte additive in LiBs and a functional scaffold for DNA-Encoded Libraries (DEL).

목차 (Table of Contents)

• Part I. Background 1
• 1.1. Hydrometallurgy 1
• 1.1.1. Introduction of Hydrometallurgy 1
• 1.1.2. Process Metallurgy 3
• 1.1.3. Waste LiBs Recycling Process 5
• 1.1.4. Organic Extractants 10
• 1.2. Sulfur(VI) Fluoride Exchange (SuFEx) Compounds 12
• 1.2.1. Introduction of SuFEx 12
• 1.2.2. SuFEx Compounds for Synthetic Utility 14
• 1.2.3. SuFEx Compounds for LiBs 17
• 1.2.4. SuFEx Compounds for Polymer 20
• 1.3. Flow Reaction 22
• 1.3.1. Introduction of Flow Reaction and Reactor 22
• 1.3.2. Synthetic Examples with Flow System 26
• Part II. From Molecular Design to Automated Manganese Extraction 31
• Chapter 1. Integrated Experimental and Computational Approaches for Designing Novel Extractants 31
• 2.1.1. Introduction of Manganese 31
• 2.1.2. Results and Discussion 34
• 2.1.3. DFT Study on Extractant Properties 46
• Chapter 2. Novel Automated Manganese Extraction via Advanced Flow Reactor 50
• 2.2.1. Introduction of Automated System for Extraction 50
• 2.1.2. Results and Discussion 52
• Part II. Conclusion 58
• Part III. Design and Application of Extractants for Selective Separation 59
• Chapter 1. Development of Organophosphorus(V) Extractants for Selective Nickel Separation 59
• 3.1.1. Introduction of Nickel 59
• 3.1.2. Synthesis of Phosphorodithioate Extractants 61
• 3.1.3. Characterization of Phosphorodithioate Extractants 64
• 3.1.4. Hydrometallurgical Process with Novel Designed Organophosphorus(V) Extractants 79
• 3.1.5. DFT Study on Extractant Properties and Selectivity 96
• 3.1.6. Applications 99
• Chapter 2. Development of Synergistic Extractants for Selective Lithium Separation 103
• 3.2.1. Introduction of Lithium 103
• 3.2.2. Synthesis of 1,3-Diketones 105
• 3.2.3. Results and Discussion 108
• 3.2.4. Mechanistic Study of Lithium Extraction 113
• Part III. Conclusion 117
• Part IV. Applications for Organic Compounds 118
• Chapter 1. Development of SuFEx Compounds for Applications 118
• 4.1.1. Introduction of SuFEx 118
• 4.1.2. Previous Study 120
• 4.1.3. Substrate Scope 122
• 4.1.4. Applications for SuFEx Compounds 129
• Chapter 2. Development of Continuous Flow Allylation Reaction 135
• 4.2.1. Introduction of Flow Reaction 135
• 4.2.2. Previous Study 136
• 4.2.3. Results and Discussion 137
• Part IV. Conclusion 142
• Part V. References 143
• Part VI. Appendix 167