現今，穩定的摻雜製程都使用相當大的有毒和易燃反應物，使用氣 - 液 - 固（VLS）生長或激光催化生長（LCG），如SiH4，PH3和B2H6。取代具有安全性問題的傳統製程是無法避免的。在這項研究中，我們開發了一種簡便的一鍋溶液合成方法，通過超臨界流體 - 液 - 固（SFLS）一步合成出磷摻雜的矽奈米線，可以有效地避免危險的前驅物，並且能展現出優異的導電性。製作成奈米線織布在不含任何導電添加劑、銅箔和黏著劑的幫助下，依然能展現出優異的電池充放性能。例如，在0.1C的充放電速率下可以展現約為1500 mA h g-1的可逆電容量表現。另外在快充的表現下，透過 Si / CNT雙層奈米織布，它可以承受高電流密度( 1C )並保持1000次循環的穩定性能。最後拆開電池，我們能清楚地觀察到整體的形貌依然相當完整，而且磷也與反應前一樣依然均勻地分布在矽奈米線之中。
鉀離子電池（PIBs）作為替代鋰離子電池（LIBs）是相當具有潛力的，因為鉀是一種豐富的化學元素（地殼中含量約為2.09％），是鋰的1000倍以上，而且鉀的標準還原電位（-2.93V v.s Eo）接近鋰（-3.04V v.s Eo），可以使我們的平均工作電壓並不會與鋰離子電池相差太多。本研究利用簡單的一鍋法直接合成出鉍為晶種的淚滴狀磷化錫奈米粒子（BiSnP）應用於鉀離子電池中。與純磷相比，BiSnP可以表現出更好的電池循環效能。例如，BiSnP / C電極在500 mA g-1的電流密度下可以展現出高達200圈的循環性能，並且在7500 mA g-1的超高電流密度下依然擁有120 mA h g-1的平均比電容量。此外，由BiSnP / C和per四羧酸二酐（PTCDA）組成的鉀離子全電池也可以展現出相當好的循環壽命。為了使實驗更加真實，我們製作成軟包式的全電池，能表現出大約4.5 mA h的容量，而且也能成功驅動超過55顆的LED燈泡。

Today, the stable doping process all use considerably toxic and flammable reactants by using vapor–liquid–solid (VLS) growth or laser catalytic growth (LCG) such as SiH4, PH3 and B2H6. Alternative to replace the traditional process can't be avoided. Otherwise, the issue of security is bound to be discussed all the time.
In this study, we report a facile one-pot solution synthesis to produce phosphorus doped silicon nanowires. Avoiding dangerous reactants, we can also produce highly doped silicon nanowires by supercritical fluid-liquid-solid (SFLS) and it can exhibit superior electrical conductivity. The nanowires solution can easily drop on the Teflon mold to manufacture the nanowires fabric as negative electrode in the lithium-ion battery without conductivity additives, Cu foil and binder. The phosphorus doped silicon nanowires fabric possesses excellent electrochemical properties with reversible capacity of roughly 1500 mA g-1 at 0.1C and the cycle life can maintain stably without decay. The Si/CNT bilayer fabric even show great rate capability. It can endure high current density and keep stable performance for 1000 cycles. We disassembled the cell after 1000 cycles, and we can find that the overall structure is the same to the original appearance without fracture during the lithiation and delithiation.
Potassium-ion batteries (PIBs) are interesting as one of the alternative metal-ion battery systems to replace lithium-ion batteries (LIBs) because potassium is an abundant chemical element (2.09% in the Earth’s crust) which is close to sodium (2.36% in the Earth’s crust) and the standard reduction potential of K (-2.93V vs Eo) is close to lithium (-3.04V vs Eo) And then, the Stoke’s radius of K-ions is the smallest as compared to Li-ions and Na-ions in the electrode of PC.
Herein, we report a facile one-pot synthesis of Bi-seeded teardrop-shaped SnP0.94 nanoparticles (BiSnP) to apply for PIBs. Compared with the P, BiSnP can exhibit better
II
electronic conductivity and may show a synergistic effect that can comprehensively improve the stability of PIBs, in comparison to the single element structure. At the same time, with the wet ball-milling process, we can obtain outstanding electrochemical performance. The BiSnP/C electrode can show great cycling performance over 200 cycles at the current density of 500 mA h g-1 and exhibit average specific capacity of 120mA h g-1 at the current density of 7500 mA h g-1. This condition shows that the overall rate capability is quite stable.
In addition, the PIBs full cell, composed of BiSnP/C anode and a perylenetetracarboxylic dianhydride (PTCDA) cathode, can also show quite good rate capability and cycling life. In order to make the experiment more realistic, we even built a pouch-type battery, expressing a capacity of roughly 4.5 mA h. It can successfully light up more than 55 LED bulbs with red, yellow and green that need voltage ~ 3V.

中文摘要 I
Abstract II
Table of contents IV
List of Figure VI
List of Table IX
Chapter 1 Synthesis and energy storage applications of P-doped silicon nanowires 2
1.1 Introduction 2
1.2 Experimental Section 7
1.2.2 Materials 7
1.2.2 Red phosphorus nanoparticles synthesis 7
1.2.3 P doped Si Nanowires Synthesis 8
1.2.4 P Doped Si Nanowires Surface Passivation 8
1.2.5 Preparation of P Doped Si Nanowire and Si/CNT Nanowire Fabric Electrode 9
1.2.6 Lithium Ion Battery Assembly and Electrochemical Characterization 9
1.2.7 Experimental Analysis 10
1.3 Result and Discussion 11
1.3.1 Characterization of Si Doped P Nanowires 11
1.3.2 Electrochemical performance 15
1.4 Conclusion 24
1.5 Reference 25
Chapter 2 Synthesis and energy storage applications of 28
teardrop-shaped SnP0.94 nanoparticles 28
2.1 Introduction 28
2.2 Experimental Section 36
2.2.1 Materials 36
2.2.2 Preparation of 0.02M bismuth precursor solution 36
2.2.3 Synthesis of tin phosphide in supercritical fluid toluene in a batch 37
2.2.4 Fabrication of SnP nanoparticles /C electrode 37
2.2.5 Potassium Ion Battery Assembly and Electrochemical Characterization 38
2.2.7 Fabrication of thermal PTCDA /C electrode 38
2.2.9 Experimental Analysis 39
2.3 Result and Discussion 40
2.4 Conclusion 59
2.5 Reference 60

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