高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (2): 366.doi: 10.7503/cjcu20200598
收稿日期:
2020-08-24
出版日期:
2021-02-10
发布日期:
2020-12-25
通讯作者:
黄长水
E-mail:huangcs@qibebt.ac.cn
基金资助:
SUN Quanhu1,2, LU Tiantian1, HE Jianjiang1, HUANG Changshui1,2()
Received:
2020-08-24
Online:
2021-02-10
Published:
2020-12-25
Contact:
HUANG Changshui
E-mail:huangcs@qibebt.ac.cn
摘要:
碳材料具有价格低廉、 易制备、 环境友好、 导电性高、 比表面积大以及适合离子存储和迁移等优点, 已成为目前应用于电化学储能器件电极的重要材料之一. 石墨炔(GDY)是一种新型的二维碳同素异形体, 由sp2碳杂化形式的苯环和sp碳杂化形式的炔键构成. 这种独特的化学结构一方面保持了碳材料良好的导电特性, 另一方面形成了新颖的离子传输通道, 为碳材料带来了不同的离子传输和存储特性. 与此同时, 由于石墨炔的空间结构可调性, 可以通过引入异原子微调石墨炔电子结构, 拓展石墨炔在电极材料领域的应用. 本文重点对近几年异原子杂化石墨炔基电极材料在锂离子电池、 钠离子电池、 金属硫电池、 电容器、 金属空气电池和电极保护等储能领域的研究工作进行总结, 并对未来石墨炔类材料在储能领域的发展进行了展望.
中图分类号:
TrendMD:
孙全虎, 卢天天, 何建江, 黄长水. 含异原子石墨炔基电极材料的研究进展. 高等学校化学学报, 2021, 42(2): 366.
SUN Quanhu, LU Tiantian, HE Jianjiang, HUANG Changshui. Advances in the Study of Heteratomic Graphdiyne Electrode Materials. Chem. J. Chinese Universities, 2021, 42(2): 366.
Fig.1 Synthetic route and SEM images of graphdiyne films(A) Synthetic route of graphdiyne films; (B) SEM image of cracked film on the brim of copper foil[4]; schematic representation N doping process of GDY(the unit structure of GDY molecule is shown as the inset)(C); (D—G) surface-(D, F) and cross-sectional(E, G) SEM images of GDY(D, E) and N-GDY(F, G)[13].(A, B) Copyright 2010, Royal Society of Chemistry; (C—G) Copyright 2016, American Chemical Society.
Fig.2 Structure and lithium ions storage performance of GDY and F?GDY(A) Structure of GDY[12]. Copyright 2019, The Royal Society of Chemistry. (B) Cycle performance of the GDY-1, GDY-2, and GDY-3 electrodes at a current density of 500 mA/g between 5 mV and 3 V; (C) rate performance of the GDY-1 electrode[18]. Copyright 2015, Elsevier. (D) Structure of F-GDY; (E, F) cycle performance of F-GDY at current densities of 50 mA/g(E) and 2 A/g(F)[24]. Copyright 2018, The Royal Society of Chemistry.
Fig.3 Structural characteristics and lithium storage performance of PY?GDY, PM?GDY, MsGDY and GDY?MoS2(A) Synthetic procedure of PY-GDY and PM-GDY; (B) photograph showing that a wearable soft package battery wrapped around a human hand can light up a LED lamp; (C, D) cycle performance of PY-GDY and PM-GDY-based electrodes at a current densities of 500 mA/g, respectively[27]. Copyright 2018, American Chemical Society. (E) Schematic diagram for the molecular fragment of MsGDY; (F) region from methyl to alkyne bond and the channel from methyl to the center; (G) experimental pore size distribution curve and simulated pore size distribution for MsGDY; (H) cycling performance of MsGDY[28]. Copyright 2020, Elsevier. (I—K) Synthetic procedure(I), rate capability(J) and cycling performance(K) of GDY-MoS2 hybrid nanomaterial[31]. Copyright 2019, Elsevier.
Fig.4 Sodium storage advantage of GDY?NS, HsGDY and BGDY materials(A) Top-view image of GDY-NS on the Cu substrate; (B) schematic illustration of the structure of GDY-NS on a Cu substrate; (C) cycle performance of the product-based electrodes at the current density of 1 A/g[37]. Copyright 2017, American Chemical Society. (D) The possible Na storage sites in BGDY; (E) rate performance of the electrode for NIBs[38]. Copyright 2018, Wiley-VCH. (F) Structure and appearance of HsGDY; (G) diffusion path of Li ions and Na ions in carbon-rich framework; (H) cycle performance of flexible electrode at the current density of 0.1 A/g[39]. Copyright 2017, The Author(s).
Sample | Device | Capacity/(mA·h·g-1) | Current density/(mA·g-1) | Cycle | Ref. |
---|---|---|---|---|---|
Cl?GDY | LIBs | 750 | 200 | 170 | [ |
N?GDY | LIBs | 785 | 200 | 200 | [ |
P?GDY | LIBs | 1169 | 50 | 50 | [ |
S?GDY | LIBs | 380 | 2000 | 1000 | [ |
F?GDY | LIBs | 490 | 2000 | 2500 | [ |
PY?GDY | LIBs | 764 | 5000 | 1500 | [ |
PM?GDY | LIBs | 483 | 5000 | 4000 | [ |
MsGDY | LIBs | 1020 | 50 | 40 | [ |
H1F1?GDY | LIBs | 2050 | 50 | 50 | [ |
GDY?MoS2 | LIBs | 1450 | 50 | 100 | [ |
GDY?NS | SIBs | 405 | 1000 | 1000 | [ |
BGDY | SIBs | 180 | 5000 | 4000 | [ |
HsGDY | SIBs | 1050 | 100 | 100 | [ |
HsGY | SIBs | 600 | 100 | 100 | [ |
Table 1 Summary of the performance of GDY-based electrodes in electrochemical batteries
Sample | Device | Capacity/(mA·h·g-1) | Current density/(mA·g-1) | Cycle | Ref. |
---|---|---|---|---|---|
Cl?GDY | LIBs | 750 | 200 | 170 | [ |
N?GDY | LIBs | 785 | 200 | 200 | [ |
P?GDY | LIBs | 1169 | 50 | 50 | [ |
S?GDY | LIBs | 380 | 2000 | 1000 | [ |
F?GDY | LIBs | 490 | 2000 | 2500 | [ |
PY?GDY | LIBs | 764 | 5000 | 1500 | [ |
PM?GDY | LIBs | 483 | 5000 | 4000 | [ |
MsGDY | LIBs | 1020 | 50 | 40 | [ |
H1F1?GDY | LIBs | 2050 | 50 | 50 | [ |
GDY?MoS2 | LIBs | 1450 | 50 | 100 | [ |
GDY?NS | SIBs | 405 | 1000 | 1000 | [ |
BGDY | SIBs | 180 | 5000 | 4000 | [ |
HsGDY | SIBs | 1050 | 100 | 100 | [ |
HsGY | SIBs | 600 | 100 | 100 | [ |
Fig.5 Application of GDY in lithium sulfur battery and lithium ion capacitor(A) Preparation of GDY-modulated PP separator; (B) as-prepared GDY-PP and separators based Li-S cells after 300 cycles; (C) color contrast of PSs solution in the left-side chambers and colourless electrolyte in the right-side chamber[47]. Copyright 2019, American Chemical Society. (D) Work mechanism between polysulfides and GDY including chemical adsorption and physical obstruction; (E) cycle performance with PI, PI-SP, and PI-GDY separators at 0.5 C[48]. Copyright 2019, American Chemical Society. (F) Suppositional lithium ions diffusion in hierarchical porous GDY-NW; (G) cycle performance of the GDY-NW at the current density of 1 A/g[49]. Copyright 2017, Elsevier.
Fig.6 N?doped GDY and transition metal doped GDY applied for Zn?air batteries(A) Pyridinic nitrogen-doped hydrogen-substituted graphdiyne(N-HsGDY); (B) a reaction equation and enthalpy change for substituting C on the inside of HsGDY with pyridinic N; (C) linear sweep voltammetry curves of pyridinic nitrogen-doped hydrogen-substituted graphdiyne treated at 900 ℃[57]. Copyright 2017, the Author(s). (D) A fragment of PyN-GDY, eight possible C active sites for ORR; (E) XPS spectra of PyN-GDY; (F) RDE polarization curves of PyN-GDY and Pt/C(JM) in O2-saturated 0.1 mol/L KOH solution at a rotating speed of 1600 r/min with a scan rate of 5 mV/s; (G—I) open-circuit voltage(G), discharge polarization curve and corresponding power density curve(H) and discharge curves at a current density of 20 mA/cm2(I) of Zn-air batteries using PyN-GDY and Pt/C air electrode; (J) rechargeability cycling tests of the Zn-air batteries using PyN-GDY as cathode at current density of 5 mA/cm2[58]. Copyright 2020, Elsevier.
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