臺灣博碩士論文加值系統

本論文研製之介相碳微球具備液晶特性，是一個製造碳材料優良的前驅物，除了優異的可壓縮性，介相碳微球因為表面駐留β-樹脂的成分，擁有良好的流動性和高燒結能力。因此，介相碳微球可經由等靜壓成型、碳化和石墨化等程序可製備高強度、高密度的等方性石墨產品；且其產品物件可直接建模成型，大幅減少傳統製程中銑削/研磨的加工需求，降低生產成本。然而，介相碳微球的自身燒結技術尚未發展完全，原料中β-樹脂的組成及含量隨著介相碳微球製備程序的改變而不同，介相碳微球的形狀和顆粒大小，往往也會影響這種非均質的燒結反應，因此相關因素對塊狀混合物的流動性和生產高品質石墨部件的影響並未完全釐清，仍待進一步開發研究。
在本文中，藉由非常精細且不同尺寸的介相碳微球與含有高β-樹脂含量的固體樹脂混合，固定不同樣品中β-樹脂的組成，進行石墨產品的製備，以探討原料接觸型式和β-樹脂含量對燒結反應和產品的影響。結果顯示，介相碳微球的自燒結反應與原料混合物的接觸型式有顯著關係，另一方面，增加β-樹脂含量可提高碳材料製品的彎曲強度；但是β-樹脂含量仍有最高容許量的限制，過多的β-樹脂含量，除了導致產品的密度降低，亦會造成樣本模型在燒結過程中爆裂。由介相碳微球製備高密度的石墨製品，最佳的β-樹脂含量大約為5.0 wt％。
介相炭燒結製品具有高密度及良好的摩擦特性，但是他們的機械強度仍無法被接受。高β-樹脂含量有助於促進燒結時介相碳微球原料的流動性，提昇介相碳微球之間的連結及產品的機械強度。所以介相碳微球原材料的β-樹脂的容許含量必須提高。在本文中，以碳黑和甲基丙烯酸縮水甘油酯用來當作聯合反應促進劑來修飾β-樹脂的燒結行為，成功的增加β-樹脂的容許含量至14.4-15.2 wt％，並製備介相炭燒結(1300°C)產品的彎曲強度和密度分別達到142 MPa以及1.87g cm-3。
此外，不同於一般製程，在介相碳微球之中混摻各種無機添加劑製備石墨複合物，本研究利用有機添加劑：雙酚Ａ，甲基丙烯酸縮水甘油酯和碳黑等作為促進劑，修飾介相碳微球的燒結行為，進行石墨化(2800°C)製成高性能純石墨塊材，改善了含無機添加劑的石墨複合物通常導致原本石墨高導熱性和導電性，低摩擦係數和優異的穩定性等優點下降的困擾。所製備的純石墨塊材，具有高導電率（892 S cm-1），高彎曲強度（62 MPa）和高密度（2.156 g cm-3）的特性。
另一方面，本文研究低β-樹脂含量的介相碳微球，應用於高倍率鋰離子電池的負極材料，結果顯示，1300°C下所製備介相軟炭具有比介相石墨更寬廣的層間間距，比商用硬炭更高的方向性，使得其顯現出最佳的高倍率充放電能力。這些事實表明，在較低溫下產生的介相軟炭可以是高倍率鋰離子電池負極材料的一個更經濟的選擇。

Mesocarbon microbeads (MCMBs), prepared from coal tar pitch, are excellent precursors for carbon materials manufacturing as a result of their liquid crystal properties. As well their excellent compressibility: the β-resin contents, residing on the surface of the MCMBs, promote fluidity and the self-sintering-ability of the clumpy mixtures. Cold isostatic pressing, carbonization and graphitization of MCMBs can be used to prepare high strength, high density isotropic graphite-thereby enabling the direct modeling of objects, while saving on expenditure, due to a reduction in the number of milling/grinding steps needed. However, the techniques needed for the self-sintering of MCMBs are not yet fully developed, due to the various β-resin components on the MCMBs being subject to variation by changes in the preparation procedures. The shapes and particle sizes of the MCMBs affects non-homogeneous sintering reactions; consequently, factors affecting the fluidity of the clumpy mixtures and the production of high-quality of graphite-parts have not been fully clarified and therefore need further investigation.
In this work, using variously sized MCMBs mixed with a high β-resin content solid-resin, fixed compositions of β-resin in different graphite products were prepared to explore the effect of the sintering reaction on the resulting products and the relationship between the contacting-pattern of the raw material mixtures and the β-resin contents. The results indicate that the self-sintering reactions of MCMBs have a significant relationship with the contacting-pattern of the raw material mixtures. While MCMBs with higher β-resin contents were found to improve the bending strength of the carbon products, the maximum allowable β-resin contents is still limited as excessive β-resin contents, in addition to giving a reduced product density, will cause the sample mold to burst during sintering. To prepare higher density graphite products, the optimum β-resin content of the MCMB mixtures needed is about 5.0 wt%.
Sintered mesocarbon products have high densities and good friction characteristics, but their mechanical strength is still not acceptable. Higher β-resin contents can promote fluidity of the raw materials and also affect neck-formation between the MCMBs, and the product’s, resulting in alterations to the product’s strength. Therefore we need the maximum allowable β-resin contents to be increased. In this paper, carbon black (CB) and glycidyl methacrylate (GMA) were used as a joint reaction-promoter. The sintering behavior of the β-resin was successfully modified to permit an increase in the β-resin contents to 14.4-15.2 wt%, which allowed carbonized carbon blocks with high bending strengths (142 MPa) and high densities (1.87 g cm-3) to be prepared.
In this study the organic additives: bisphenol A, GMA and CB were used as promoters to modify the sintering behavior of MCMBs with additional heat treatment (2800°C) to prepare high performance graphite blocks. The disadvantages of graphite-containing inorganic additives typically manifest as decline in the desired properties of the original graphite composite’s high thermal and electrical conductivity, low coefficient of friction and excellent stability. Pure graphite blocks with high electrical conductivities (892 S cm-1), high bending strengths (62 MPa) and high densities (2.156 g cm-3) were prepared in this study.
This study showed an improvement in MCMBs, with low β-resin contents, when used as anode materials in high C-rate LIBs. The results showed that the mesophase soft carbon, made from MCMBs at 1300°C, has a wider interlayer spacing compared to mesophase graphite, made from MCMBs at 2800°C, and is highly oriented in comparison with commercial hard carbon, giving it the best high C-rate charge and discharge capacity. These facts indicate that the mesophase soft carbon produced at lower temperatures can be an economical choice for high C-rate LIBs anode materials.

摘要 i
ABSTRACT iii
誌 謝 vi
Table of Contents vii
List of Tables x
List of Figures xi
Chapter 1 Background and Purpose 1
1.1 Introduction 1
1.2 MCMBs 4
1.2.1 Growth mechanisms 7
1.2.2 Preparation procedure 9
1.3 Graphite 10
1.3.1 Properties 10
1.3.2 Preparation 13
1.4 MCMBs as raw materials for carbon/graphite blocks 13
1.4.1 Self-sintering behavior of MCMBs 14
1.4.2 The effects of molding on the performance of the products 16
1.4.3 The effects of heat-treatment on the performance of the products 20
1.5 MCMBs as raw materials for LIB anodes 22
1.5.1 Working principle of LIBs 22
1.5.2 The performance of graphitized MCMBs for use as anode materials in LIB 24
1.6 Study purpose and description 28
Chapter2 Improving the sintering properties of MCMB raw materials for the manufacture of high performance carbon/graphite blocks-contacting pattern and optimum β-resin contents 31
2.1 Introduction 32
2.2 Experimental 35
2.2.1 Characteristics of the MCMBs, the solid resins and the carbon-blocks 35
2.2.2 Carbonization and graphitization of carbon-blocks 38
2.3 Results and discussion 39
2.3.1 Carbonization of the carbon-blocks 39
2.3.2 Graphitization 48
2.4 Conclusions 53
Chapter 3 Modify the sintering behavior of MCMB materials for the manufacture of carbon/graphite blocks with promoters 54
3.1 Introduction 54
3.2 Experimental Details 57
3.3 Results and discussion 58
3.3.1 Effects of GMA and CB on the molecular weight distribution and β-resin content of the heated solid-resin 58
3.3.2 TGA/DTA behavior of the solid-resin with and without GMA and CB 62
3.3.3 Improvement of bending strength and density of the carbonized carbon blocks in the presence of CB and GMA 64
3.4 Conclusions 69
Chapter 4 Preparation of high quality pure graphite block from organic- promoters modified MCMBs 71
4.1 Introduction 71
4.2 Experimental 73
4.3 Results and discussion 75
4.3.1 Thermal behavior of SR material and their effects on the sintered MCMB product qualities 75
4.3.2 Properties and characteristics of pure graphite products from the MCMB raw materials modified by the various organic additives 82
4.4 Conclusions 89
Chapter 5 Preparation of advanced carbon anode materials from MCMBs for use in high C-rate LIBs 91
5.1. Introduction 91
5.2. Experimental 93
5.2.1. Materials and instrumentations 93
5.2.2. Electrochemical analysis 95
5.3. Results and discussion 96
5.4. Conclusions 109
Chapter 6 Conclusions 111
References 115
作者簡歷 126

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