An innovative and efficient method for the preparation of mesocarbon microbeads and their use in the electrodes of lithium ion batteries and electric double layer capacitors
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摘要: 基于沥青在熔融纺丝过程中的滴落行为和流变学理论,提出了一种新型高效的中间相炭微球(MCMB)制备方法—毛细管破裂法(DCB法)。本实验以中间相沥青为原料,采用DCB法考察了不同接收相(水或THF)对MCMB制备的影响规律,并系统研究了相应MCMB微观结构的演变规律。在此基础上,所制MCMB经750 °C的KOH活化制备了A-MCMB,以及经2800 °C的石墨化制备了G-MCMB,并分别探究了它们作为超级电容器(EDLC)和锂离子电池(LIB)电极材料的电化学性能。结果表明:采用DCB方法所制备的水接收相的MCMB-W和THF接收相的MCMB-T均呈现尺寸约1~2 μm的球形结构特征。此外,A-MCMB-T具有高比表面积1391 m2 g−1、微孔体积0.55 cm3 g−1和中孔体积0.24 cm3 g−1,作为EDLC的电极材料时,其比电容比MP衍生的炭材料提高了30%,且电容保持率也显著提升。同时,G-MCMB-T具有较高的石墨化度0.895和有序的层状结构,作为LIB的负极材料时,在100 mA g−1下进行100次循环后,具有353.5 mAh g−1的高比容量。因此,本文提出并验证了一种新的MCMB制备方法,有望为储能材料的设计和开发提供了一种思路和途径。Abstract: An innovative and efficient method for preparation of mesocarbon microbeads (MCMBs) was developed based on the dripping behavior and rheological properties of molten pitch during melt-spinning, where a string of beads was formed after the pitch was extruded from spinnerets and dropped into a receiving solvent (tetrohydrofuran or water). The pitch droplets were first carbonized, then activated by KOH or graphitized at 2800 °C to prepare A-MCMBs or G-MCMBs, respectively, and these were respectively used as the electrode materials for electric double layer capacitors (EDLCs) and lithium-ion batteries (LIBs). Results showed that both MCMB-W prepared using water as the receiving solvent and MCMB-T prepared using tetrohydrofuran as the receiving solvent had a spherical shape with sizes of 1-2 μm. A-MCMB-T had a high specific surface area (1 391 m2 g−1), micropore volume (0.55 cm3 g−1) and mesopore volume (0.24 cm3 g−1), with a 30% higher specific capacitance than an activated mesophase carbon prepared under the same conditions, and its capacitance retention was significantly improved when it was used as an electrode material for EDLCs. G-MCMB-T had a high degree of graphitization (0.895) and when it was used as an electrode material for LIBs it had a high specific capacity of 353.5 mAh g−1 after 100 cycles at 100 mA g−1. This work reports a new preparation method for MCMBs, which could be used to prepare energy storage materials.
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Table 1. Relevant analysis results of samples
Samples Yield TG (in N2) DSC (in air) FTIR Raman Td
(°C)W △T
(°C)△H
(J/g)△H/△T IOS ICHS IA ID/IG IA/IG MP ─ 235 54% 207 291 1.41 0.225 0.501 0.503 0.69 0.40 MS-W ─ 241 52% 218 405 1.86 0.224 0.500 0.502 0.64 0.35 MS-T ─ 305 72% 221 209 0.95 0.212 0.498 0.501 0.60 0.32 O-MP 103% 291 77% ─ ─ ─ 0.243 0.500 0.500 0.83 0.45 O-MS-W 104% 296 77% ─ ─ ─ 0.241 0.495 0.501 0.69 0.38 O-MS-T 105% 301 80% ─ ─ ─ 0.239 0.494 0.499 0.62 0.33 C-MP 70% ─ ─ ─ ─ ─ 0.250 0.499 0.500 1.14 0.53 C-MS-W 72% ─ ─ ─ ─ ─ 0.249 0.498 0.499 1.12 0.51 C-MS-T 74% ─ ─ ─ ─ ─ 0.247 0.497 0.498 1.08 0.45 Table 2. Microstructure and porosity parameters of A-MCMBs
Samples Raman Parameters of pore structure ID/IG IA/IG SBET
(m2 g−1)Vmic
(cm3 g−1)Vmes
(cm3 g−1)Vtot
(cm3 g−1)D
(nm)A-MP 0.99 0.60 1222 0.16 0.49 0.65 5.04 A-MS-W 0.96 0.71 1190 0.33 0.17 0.50 5.00 A-MS-T 0.94 0.72 1391 0.37 0.24 0.61 4.19 Table 3. FTIR and XPS analysis results of A-MCMBs
Samples FTIR XPS (at%) percentage of total C1s percentage of total O1s IOS ICHS IA C O C=C C―O C=O COOH C=O C―O COOH A-MP 0.251 0.500 0.502 90.03 8.70 35.29 23.73 19.85 21.13 31.66 35.91 32.43 A-MS-W 0.231 0.480 0.482 90.45 8.39 35.26 23.75 19.87 21.12 32.46 36.04 31.50 A-MS-T 0.220 0.460 0.462 91.28 7.64 34.32 24.28 21.27 20.13 32.96 37.20 29.84 Table 4. Electrochemical properties of different A-MCMBs
Samples Specific capacitance(F/g) Capacitance retention(%) Rct(Ω) 0.5 A g−1 1 A g−1 2 A g−1 5 A g−1 10 A g−1 A-MP 156.9 131.1 118.8 108.5 100.0 63.7 0.6 A-MS-W 178.6 169.5 153.4 145.0 139.0 77.8 0.5 A-MS-T 193.5 166.2 147.0 135.5 129.0 66.6 0.3 Table 5. Parameters of pore structure and graphite microcrystallite s of G-MCMBs
Samples ID/IG ID’/IG SBET
(m2 g−1)d002
(nm)Lc
(nm)La
(nm)N
(n)G G-MP 0.21 0.05 1.60 0.3366 0.6582 1.3976 2.96 0.861 G-MS-W 0.18 0.04 2.25 0.3366 0.6973 1.9862 3.07 0.861 G-MS-T 0.14 0.02 3.53 0.3363 0.5680 2.4556 2.69 0.895 Table 6. Cycle performance of different G-MCMBs
Samples Specific capacity (mAh g−1) ICE
(%)
Capacity retention
(%)Rct
(Ω)D1 C1 D2 D3 D100 G-MP 329.4 277.6 285.1 277.1 255.3 84.27 77.50 295.9 G-MS-W 401.4 346.9 354.0 349.6 313.6 86.42 78.13 301.9 G-MS-T 408.1 353.0 366.6 362.4 353.5 86.50 86.62 95.5 -
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Supporting Information ——20220001.pdf