收稿日期: 2020-01-10
网络出版日期: 2022-03-02
基金资助
国家自然科学基金资助项目(21406136);上海市教委科研创新资助项目(14YZ015);创新团队发展计划资助项目(IRT13078);上海智能计算系统工程技术研究中心资助项目(19DZ2252600)
Adsorption and transport properties of the lithium ion in a covalent organic framework/carbon nanotube composite by molecular simulation
Received date: 2020-01-10
Online published: 2022-03-02
利用分子模拟方法对共价有机骨架 (covalent organic framework, COF)/碳纳米管(carbon nanotube, CNT) 复合材料 COF@CNT 中锂离子 (Li$^{+})$ 的吸附与传输特性开展研究, 明确了 Li$^{+}$ 的吸附位点与吸附顺序, 得到了相应的吸附能, 并观察 COF@CNT 的表观形貌变化. 当达到饱和吸附状态时, COF@CNT 的体积变化率仅为 0.25, 平均电压保持在 2.00 V 以上, 而理论容量则高达 1 402.47 mAh/g. 此外, Li$^{+}$ 在 COF@CNT 内部的电导率大于其在单纯 CNT 中电导率的实测值. 模拟结果可为此类体系的实际应用提供理论基础.
徐毅, 崔致远, 吴凡, 袁彬 . 共价有机骨架/碳纳米管复合材料中锂离子吸附与传输特性的分子模拟[J]. 上海大学学报(自然科学版), 2022 , 28(1) : 91 -101 . DOI: 10.12066/j.issn.1007-2861.2224
In this study, the adsorption and transport properties of the lithium ion (Li$^{+})$ in a covalent organic framework/carbon nanotube composite (COF@CNT) are investigated through molecular simulation. The adsorption sites and sequence of Li$^{+}$ are defined and the corresponding adsorption energy is obtained. In addition, apparent change in the morphology of the COF@CNT is identified. When saturated adsorption is reached, the volumetric change rate of the COF@CNT is only 0.25. Simultaneously, the average voltage is maintained at greater than 2.00 V, and the theoretical capacity reaches as high as1402.47 mAh/g. Finally, the electronic conductivity of Li$^{+}$ inside the COF@CNT exceeds that in a pure CNT. The results of this study can provide a theoretical basis for the practical application of these systems.
| [1] | Wang Y, Wu Y C, Xie J, et al. Multi-walled carbon nanotubes and metal-organic framework nanocomposites as novel hybrid electrode materials for the determination of nano-molar levels of lead in a lab-on-valve format[J]. Analyst, 2013, 138(17): 5113-5120. |
| [2] | Yue Y F, Guo B K, Qiao Z A, et al. Multiwall carbon nanotube@zeolite imidazolate framework composite from a nanoscale zinc oxide precursor[J]. Microporous and Mesoporous Materials, 2014, 198: 139-143. |
| [3] | Xu F, Jin S B, Zhong H, et al. Electrochemically active, crystalline, mesoporous covalent organic frameworks on carbon nanotubes for synergistic lithium-ion battery energy storage[J]. Scientific Reports, 2015, 5: 08225. |
| [4] | Zhang Y D, Lin B P, Sun Y, et al. Carbon nanotubes@metal-organic frameworks as Mn-based symmetrical supercapacitor electrodes for enhanced charge storage[J]. RSC Advances, 2015, 5(72): 58100-58106. |
| [5] | Wen P, Gong P W, Sun J F, et al. Design and synjournal of Ni-MOF_CNT composites and rGO_carbon nitride composites for an asymmetric supercapacitor with high energy and power density[J]. Journal of Materials Chemistry A, 2015, 3(26): 13874-13883. |
| [6] | Yang W X, Zhang Y L, Liu X J, et al. In situ formed Fe-N doped metal organic framework@carbon nanotubes graphene hybrids for a rechargeable Zn-air battery[J]. Chemical Communications, 2017, 53(96): 12934-12937. |
| [7] | Han Y, Zhang Q, Hu N T, et al. Core-shell nanostructure of single-wall carbon nanotubes and covalent organic frameworks for supercapacitors[J]. Chinese Chemical Letters, 2017, 28(12): 2269-2273. |
| [8] | Sun B, Liu J, Cao A M, et al. Interfacial synjournal of ordered and stable covalent organic frameworks on amino-functionalized carbon nanotubes with enhanced electrochemical performance[J]. Chemical Communications, 2017, 53(47): 6303-6306. |
| [9] | Mao Y Y, Li G R, Guo Y, et al. Foldable interpenetrated metal-organic frameworks carbon nanotubes thin film for lithium-sulfur batteries[J]. Nature Communications, 2017, 8: 14628. |
| [10] | 庄林. 基于金属有机框架和碳纳米管的可折叠锂-硫电池[J]. 物理化学学报, 2017, 33(4): 655-655. |
| [11] | Lei Z D, Yang Q S, Xu Y, et al. Boosting lithium storage in covalent organic framework via activation of 14-electron redox chemistry[J]. Nature Communications, 2018, 9: 576. |
| [12] | Xu G D, Zuo Y X, Huang B. Metal-organic framework-74-Ni carbon nanotube composite as sulfur host for high performance lithium-sulfur batteries[J]. Journal of Electroanalytical Chemistry, 2018, 830: 43-49. |
| [13] | Zhang X, Wang Z, Yao L, et al. Synjournal of core-shell covalent organic frameworks multi-walled carbon nanotubes nanocomposite and application in lithium-sulfur batteries[J]. Materials Letters, 2018, 213: 143-147. |
| [14] | Pu Y J, Wu W B, Liu J Y, et al. A defective MOF architecture threaded by interlaced carbon nanotubes for high-cycling lithium-sulfur batteries[J]. RSC Advances, 2018, 8(33): 18604-18612. |
| [15] | Chen X D, Zhang H, Ci C G, et al. Few-layered boronic ester based covalent organic frameworks/carbon nanotube composites for high-performance K-organic batteries[J]. ACS Nano, 2019, 13(3): 3600-3607. |
| [16] | 章琴, 刘帅, 姚路. 共价有机框架/多壁碳纳米管复合材料及其双电层电容器性能[J]. 微纳电子技术, 2019, 56(3): 195-199. |
| [17] | Li X, Zhou K F, Tong Z B, et al. Heightened integration of POM-based metal-organic frameworks with functionalized single-walled carbon nanotubes for superior energy storage[J]. Chemistry-An Asian Journal, 2019, 14, 3424-3430. |
| [18] | Hu Z Q, Jiang J W. Covalent-organic framework as a template to assemble carbon nanotubes into a high-density membrane: computational demonstration[J]. Nanoscale, 2014, 6: 772-777. |
| [19] | 高佳. 分子模拟技术在 COF 材料研究中的应用[D]. 兰州: 兰州大学, 2012. |
| [20] | Fang L, Cao X R, Cao Z X. Covalent organic framework with high capacity for the lithium ion battery anode: insight into intercalation of Li from first-principles calculations[J]. Journal of Physics-Condensed Matter, 2019, 31(20): 205502. |
| [21] | Aydinol M K, Kohan A F, Ceder G. Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides[J]. Physical Review B, 1997, 56(3): 1354-1365. |
| [22] | Courtney I A, Tse J S, Mao O, et al. Ab initio calculation of the lithium-tin voltage profile[J]. Physical Review B, 1998, 58(23): 15583-15588. |
| [23] | Aydinol M K, Kohan A F, Ceder G, et al. Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides[J]. Physical Review B, 1997, 56(3): 1354-1365. |
| [24] | Yi T F, Zhu Y R, Zhu R S. Density functional theory study of lithium intercalation for 5 V LiNi$_{0.5}$Mn$_{1.5}$O$_{4}$ cathode materials[J]. Solid State Ionics, 2008, 179(38): 2132-2136. |
| [25] | Miao M H. Electrical conductivity of pure carbon nanotube yarns[J]. Carbon, 2011, 49(12): 3755-3761. |
/
| 〈 |
|
〉 |
