我們研究了構型熵對二維金屬磷三硫化物 (MPS3) 在鉀離子器件中用作陽極時的循環性能的影響。通過真空固相法合成了厚度範圍為 6 至 10 nm 的高產率二維高熵 CoVMnFeZnPS3 (HEPS3)。由於各種金屬離子對 K+ 結合能的相互作用產生的高熵效應，HEPS3能夠在電極界面處實現高效的鉀離子傳輸和嵌入。HEPS3 鉀離子陽極的性能優於它們的中熵（CoMnFePS3（ME3PS3）和 CoMnFeZnPS3（ME4PS3））、CoFePS3（LE2PS3）和 FePS3（LEPS3）對應物，表現出524 mAh g-1的高可逆容量，令人印象深刻的高倍率容量高達 10 A g-1，以及超過1000次循環的出色循環穩定性。我們的研究結果表明，HEPS3在循環過程中的電化學重構對於實現高性能鉀離子電池至關重要。原位形成的金屬合金層充當催化劑，不僅提供合適的吸附能以防止穿梭效應，而且促進多硫化物的完全轉化。此外，均勻分散在二維平面上的陽離子產生“晶格畸變效應”，賦予結構高機械穩定性，並允許在 K+ 插入/提取過程中電極中產生的內應力均勻分佈，從而抑制電極粉化 並防止 MPCh3 層的聚合。這項工作提出了一種通過高熵層狀金屬磷化物的電化學活化顯著提高鉀離子存儲性能的新策略，從而開闢了儲能設備中二維材料設計原理的新視野。

We investigate the influence of configurational entropy on the cycling performance of 2D metal phosphorus trichalcogenides (MPS3) when utilized as anodes in potassium-ion devices. High yield, two-dimensional high-entropy CoVMnFeZnPS3 (HEPS3) with thickness ranging from 6 to 10 nm was synthesized via a vacuum solid-state method. HEPS3 enables efficient potassium-ion transport and intercalation at the interface of electrodes, thanks to the high-entropy effects arising from the interaction of various metal ions on the K+ binding energy. HEPS3 potassium-ion anodes outperform their medium-entropy (CoMnFePS3 (ME3PS3) and CoMnFeZnPS3 (ME4PS3)), CoFePS3 (LE2PS3), and FePS3 (LEPS3) counterparts, exhibiting a high reversible capacity of 524 mAh g-1, impressive high-rate capability up to 10 A g-1, and exceptional cycling stability over 1000 cycles. Our findings indicate that the electrochemical reconstruction of HEPS3 during cycling is crucial for achieving high-performance potassium-ion batteries. In situ-formed metal alloy layers act as catalysts, offering not only suitable adsorption energy to prevent the shuttle effect but also promoting the complete conversion of polysulfides. Furthermore, cations uniformly dispersed across the 2D plane create a "lattice distortion effect," imparting the structure with high mechanical stability and allowing for even distribution of internal stress generated in the electrode during the K+ insertion/extraction process, which in turn suppresses electrode pulverization and prevents the aggregation of MPCh3 layers. This work proposes a novel strategy for significantly enhancing potassium-ion storage performance through the electrochemical activation of high-entropy layered metal phosphides, thus opening a new horizon of 2D material design principle in energy storage devices.

Table of Contents

中文摘要 i
Abstract ii
Table of contents iii
List of Tables vi
List of Figures vii
List of Supporting Figures ix
Chapter 1. High-entropy metal phosphorus trichalcogenide nanosheets boost high-performance potassium ion storage devices via electrochemical reconstruction 1
1.1 Introduction 1
1.2 Experimental Section . 5
1.2.1 Materials 5
1.2.2 Synthesis of Bulk CoVMnFeZnPS3 5
1.2.3 Synthesis of MPCH3 NS with different entropy 5
1.2.4 Synthesis of HEPS3@G composites 6
1.2.5 Synthesis of MPCH3@G composites with different entropy 6
1.2.6 Synthesis of Prussian blue (PB) 6
1.2.7 Materials Characterizations 6
1.2.8 Electrochemical Measurements 7
1.2.9 Calculation Details 8
1.2.10 Potassium-ion full cell of HEPS3@G//PB 9
1.2.11 Potassium-ion hybrid capacitor of HEPS3@G//AC 9
1.3 Result and discussion. 10
1.4 Conclusion 47
Chapter 2. Bimetallic 2D thiophosphate nanosheets as anode material for high-performance potassium ion storage devices
2.1 Introduction 48
2.2 Experimental Section. 50
2.2.1 Materials 50
2.2.2 Synthesis of CIPS 50
2.2.3 Synthesis of CIPS@G composites 51
2.2.4 Materials Characterizations 51
2.2.5 Electrochemical Measurements 52
2.2.6 Potassium-ion hybrid capacitor of CIPS@G//AC 52
2.3 Result and discussion. 53
2.4 Conclusion 66
Reference 67

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