Coal tar pitch pitch modification of the SiO interface enhances the cycling stability of lithium-ion batteries
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摘要: 煤焦油沥青具有高碳含量、可调控性和经济性等优点，在制备碳材料和碳复合材料中具有广泛的应用前景。采用沥青对一氧化硅界面改性是抑制一氧化硅自身的膨胀、提升首次库伦效率和循环稳定性的有效策略。为改善沥青与基体材料间的结合性能，本研究采用添加黏结剂的方式制备负极材料。首先，通过空气交联低温条件下制备高软化点、高结焦值的改性沥青。以聚乙烯吡咯烷酮(PVP)为黏结剂，浸润结合一氧化硅和改性沥青，制备得到前驱体(SiO@PVP@pitch)。通过原位聚合，将改性沥青转化为中间相沥青，然后高温炭化得到SiO/C复合材料，使碳涂层有一定的机械强度又具备导电性。偏光显微镜结果表明碳涂层良好的流线型结构，纤维更加细腻。高分辨透射电子显微镜( HRTEM )结果表明，SiO表面存在厚度约为90 - 100 nm的含有石墨晶格的碳包覆层。SiO和改性沥青按照5∶3比例下在400 ℃和900 ℃的温度条件下聚合和炭化，复合材料表现出优异的电化学性能，在0.5 A/g电流密度下具有550 mA·h/g的高比容量，可逆比容量660 mA·h/g，200次循环后比容量保持率为83.33 %，在1.5 A/g电流密度下的比容量为472.8 mA·h/g。电化学阻抗谱( EIS )结果也证明了碳包覆层可以有效提高复合材料的导电性，从而增强SiO电极的循环稳定性。Abstract: Coal tar pitch has the advantages of high carbon content, controllability and economy, and broad application prospects in preparing carbon materials and carbon composites. Using pitch to modify the interface of silicon monoxide is an effective strategy to inhibit the expansion of silicon monoxide itself and improve the first Coulomb efficiency and cycle stability. To improve the bonding performance between pitch and matrix materials, this study prepared anode materials by adding binders. Firstly, we prepared a modified pitch with a high softening point, high coking value, and good rheology by air crosslinking at low temperatures. The precursor (SiO@PVP@pitch) was prepared b, using polyvinylpyrrolidone (PVP) as a binder and infiltrating combined with silicon monoxide and modified pitch. Through in-situ polymerization, the modified pitch is converted into mesophase pitch and then carbonized at high temperature to obtain SiO/C composites, so that the carbon coating has certain mechanical strength and electrical conductivity. The results of the polarizing microscope show that the carbon coating has a good streamlined structure and the fiber is more delicate. High-resolution transmission electron microscopy (HRTEM) results show that there is a carbon coating layer containing graphite lattice with a thickness of about 90-100 nm on the surface of SiO. The synthesized SiO/C - 5∶3 - 4 h composites showed excellent performance. It has a high specific capacity of 550 mA·h/g at 0.5 A/g, a reversible capacity of 660 mA·h/g, and a capacity retention rate of 83.33 % after 200 cycles. The capacity is 472.8 mA·h/g at 1.5 A/g. Electrochemical impedance spectroscopy (EIS) results also prove that the carbon coating layer can effectively improve the conductivity of the composite material, thereby enhancing the cycle stability of the SiO electrode.
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Key words:
- anode /
- core-shell structure /
- mesophase pitch /
- carbon coating /
- lithium-ion battery
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图 2 SiO/C复合材料的制备过程和微观结构特征示意图。
Figure 2. The schematic diagram of the preparation process and microstructure characteristics of SiO/C composites.
图 3 复合材料的XRD图和拉曼光谱图: (a) XRD 图, (b) 拉曼光谱图
Figure 3. XRD and Raman spectra of the composites: (a) XRD, (b) Raman spectra
图 4 复合材料的偏光显微图像: (a) SiO/C - 5∶3 - 0 h复合材料偏光显微镜图像(b) SiO/C - 5∶3 - 4 h复合材料偏光显微镜图像
Figure 4. Polarizing microscope images of SiO/C-5∶3 - 0 h composites: (a) Polarizing microscope images of SiO/C -5∶3 - 0 h composites (b) Polarizing microscope images of SiO/C-5∶3 - 4 h composites
图 5 SiO/C - 5∶3 - 4 h的高分辨透射电镜(HRTEM)图像(a)、(b)和(c)为不同放大倍数下的高分辨透射电镜(HRTEM)图像(d)、(e)和(f)为碳涂层的厚度 (g) TEM - Mapping图像
Figure 5. High-resolution transmission electron microscopy (HRTEM) images (a), (b), and (c) are high-resolution transmission electron microscopy (HRTEM) images at different magnifications (d), (e) and (f) are the thickness of the carbon coating (g) TEM-Mapping images of SiO/C - 5∶3 - 4 h
图 6 SiO/C的XPS 图样：(a)元素组成 (b) O 1s、(c) N 1s、(d) C 1s和 (e) Si 2p 高分辨率图样
Figure 6. XPS patterns of SiO /C (a) elemental composition (b) O 1s, (c) N 1s, (d) C 1s, and (e) Si 2p high-resolution patterns
图 8 复合材料电化学性能图 (a)-(b) SiO/C - 5∶3 - 4 h复合材料和SiO CV曲线，电压范围为0.01 - 1.8 V，扫描速率为0.1 mV·s−1；(c) - (d) SiO/C - 5∶3 - 4 h复合材料和SiO在第1个、第2个、第3个、第100个和第200个循环的充放电电压曲线。
Figure 8. Electrochemical performance of SiO/C-5∶3-4 h composite material. (a) CV curve of SiO/C - 5∶3 - 4 h composite material, the voltage range is 0.01-1.8 V, and the scanning rate is 0.1 mV·s−1. The charge and discharge voltage curves of (c) - (d) SiO/C - 5∶3 - 4 h composites and SiO at the 1st, 2 nd, 3 rd, 100 th and 200 th cycles.
图 9 复合材料电化学性能图 (a)SiO/C复合材料在 0.5 A/g电流密度下的循环性能(b)SiO/C复合材料在不同电流密度下的倍率性能。
Figure 9. (a) Cycle performance of SiO/C composites at 0.5 A/g current density (b) Rate performance of SiO/C composites at different current densities.
图 10 SiO/C - 5∶3 - 4 h和SiO/C - 5∶3 - 0 h复合材料的长循环性能图。
Figure 10. The long cycle performance of SiO/C-5∶3 - 4 h and SiO/C-5∶3-0 h composites.
图 11 奈奎斯特图和相应的等效电路模型EIS图谱(a) SiO/C复合材料阻抗(b) SiO循环前后阻抗(c) SiO/C - 5∶3 - 4 h循环前后阻抗
Figure 11. Nyquist diagram and EIS diagram of the corresponding equivalent circuit model (a) Impedance of SiO/C composites (b) Impedance before and after SiO cycling (c) Impedance before and after SiO/C - 5∶3 - 4 h cycling
图 12 SiO和SiO/C - 5∶3 - 4 h复合材料循环前和200个循环后的电极的体积变化的SEM图像(a) SiO循环前(b) SiO循环后(c) SiO/C - 5∶3 - 4 h循环前(d) SiO/C - 5∶3 - 4 h循环后
Figure 12. SEM images of volume change of SiO and SiO/C-5∶3 - 4 h composite electrode before and after 200 cycles (a) before SiO cycle (b) after SiO cycle (c) before SiO/C-5∶3 - 4 h cycle (d) after SiO/C-5∶3 - 4 h cycle
表 1 改性沥青的制备条件
Table 1. Preparation conditions of modified pitch
Air purge air volume/(L min−1) soaking time/h The heating rate of different temperature stages/(℃min−1) 25℃ - 100℃ 100℃- 290℃ 290℃ - 320℃ 1 10 5 3 1 
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表 2 原料沥青与改性煤沥青的特性和元素分析对比表
Table 2. Characteristics and elemental analysis comparison table of raw pitch and modified coal tar pitch
Sp/℃ CV/% pitch analysis/% elementary analysis/% HS HI-TS TI-QS QI N C H S O Pitch 31 32 30.98 53.03 18.55 0.031 1.145 92.474 4.979 0.356 1.046 Modified pitch 240 80 10.77 12.37 63.85 13 1.21 92.671 4.303 0.145 2.04 Note：(1) Organic element analysis was based on air drying, and O content was calculated by subtraction method.(2) Softening point (SP) was measured by thermal mechanical analyzer;(3) Coking value (CV) was determined by ' GB/T 8727-2008 determination method of the coking value of coal tar pitch products ';(4) HS and HI-TS were measured by soxhlet extraction, where HS is n-hexane soluble, HI-TS is n-hexane insoluble-toluene soluble;(5) TI-QS is toluene insoluble-quinoline soluble, its content is the percentage minus HS, HI-TS, QI content;(6) QI content is determined by the national standard GB/T 2293-2019 quinoline insoluble test method for coking pitch products.
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表 3 SiO/C复合材料中SiO和pitch的百分比及炭化条件
Table 3. Percentages of SiO and pitch in SiO/C composites and carbonization conditions
composites materials pitch:SiO SiO content pitch content Polymerization Temperature/℃ SiO/C -5∶3 - 4 h 5∶3 37.5 % 62.5 % 400℃-4 h 900℃ - 3 h SiO/C -5∶2 - 4 h 5∶2 28.5 % 71.5 % 400℃-4 h 900℃ - 3 h SiO/C - 5∶4 - 4 h 5∶4 44.4 % 55.56 % 400℃-4 h 900℃ - 3 h SiO/C -5∶3 - 0 h 5∶3 37.5 % 62.5 % 400℃-900℃ - 3 h
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