玉米芯基碳点电化学法制备及其储钠性能

李瑞林; 赵宗彬; 冷昌宇; 李勇; 艾李申; 孙洋; 王旭珍; 邱介山

doi:10.1016/S1872-5805(22)60644-9

玉米芯基碳点电化学法制备及其储钠性能

doi: 10.1016/S1872-5805(22)60644-9

李瑞林^1,,
赵宗彬^1, ,,
冷昌宇¹,
李勇¹,
艾李申¹,
孙洋¹,
王旭珍¹,
邱介山^{1, 2, ,}

1.
大连理工大学化工学院，精细化工国家重点实验室，辽宁省能源材料化工重点实验室，辽宁大连 116024
2.
北京化工大学化学工程学院，北京 100029

基金项目: 国家自然科学基金(52172038，22179017，U1610105)。

详细信息

作者简介:
李瑞林，硕士研究生.E-mail：ruilinli2019@163.com

通讯作者:
赵宗彬，教授. E-mail：zbzhao@dlut.edu.cn

邱介山，教授. E-mail：jqiu@dlut.edu.cn

中图分类号: TQ127.1⁺1
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-23
- 修回日期: 2023-03-03
- 网络出版日期: 2022-08-23
- 刊出日期: 2023-04-07

Preparation of carbon dots from carbonized corncobs by electrochemical oxidation and their application in Na-batteries

1.
State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Energy Materials and Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
2.
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Funds: National Natural Science Foundation of China (52172038, 22179017, U1610105).

More Information

Author Bio:
LI Rui-lin, Master Student. E-mail: ruilinli2019@163.com

Corresponding author: ZHAO Zong-bin, Ph. D, Professor. E-mail: zbzhao@dlut.edu.cn; QIU Jie-shan, Ph. D, Professor. E-mail: jqiu@dlut.edu.cn

摘要

摘要: 碳点（CDs）是一种新兴的碳纳米材料，因其高比表面积、良好的分散性、丰富的表面官能团、低生物毒性和光致发光特性而受到了研究者的广泛关注。然而，低成本、大规模和绿色合成CDs仍面临挑战。本工作基于生物质玉米芯特殊的天然孔隙结构，经直接炭化制备具有定向、贯通微纳米孔道的多孔三维电极材料，在毛细作用下电解液可以充满整个电极材料，内外表面同时发生电化学氧化，实现高效制备CDs。在1 A恒电流下，每克电极材料制备CDs速率达到了79.83 mg h⁻¹。将制备的CDs与氧化石墨烯（GO）水热复合得到复合气凝胶CDs/rGO材料，经热处理后应用于钠离子电池。在1 A g⁻¹下循环1000圈仍保持263.3 mAh g⁻¹的容量。本研究工作采用生物质玉米芯高效制备CDs，为CDs的大规模绿色制备和应用提供了新的途径和思路。
- 玉米芯 /
- 碳点 /
- 电化学制备 /
- 钠离子电池
Abstract: Carbon dots (CDs) have attracted increasing attention due to their high specific surface area, good dispersion, abundant surface functional groups, low biotoxicity and photoluminescence. However, their preparation on a large-scale is still a great challenge because of the high cost and environmental problems, and this seriously limits their practical applications. Herein, carbonized corncobs were used as the starting material for the preparation of the CDs by electrochemical oxidation. Their natural porous structures with well-developed channels allow the electrode to be filled with electrolyte, and the electrochemical oxidation takes place both on the inside and outside surfaces of the carbonized corncob, achieving a CD output of 79.8 mg h⁻¹ per gram of electrode material at 1 A. The CDs were combined with graphene oxide (GO) to produce CD/rGO composite aerogels by a hydrothermal method. After heat treatment at 600 °C, the materials obtained were used as the anode in a sodium ion battery, which had a capacity of 263.3 mAh g⁻¹ after 1 000 cycles at 1 A g⁻¹. This work suggests a new way to prepare CDs and possibly expand their range of application.
- Corncob /
- Carbon dots /
- Electrochemical synthesis /
- Sodium ion batteries

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FIG. 2238. FIG. 2238.

FIG. 2238.. FIG. 2238.

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图 1 碳点的制备过程示意图

Figure 1. Illustration diagram of carbon dot preparation process

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图 2 (a) 玉米芯截面；(b-d) 炭化玉米芯各部分刻蚀前的SEM照片：(b) 中心；(c) 鞘；(d) 外层薄片；(e) 炭化玉米芯刻蚀后轴向剖面；(f-h) 玉米芯各部分刻蚀前的SEM照片：(f) 中心；(g) 鞘；(h) 外层薄片

Figure 2. (a) Cross-section of corncob; (b-d) SEM images of carbonized corncob before etching; (b) center; (c) sheath; (d) sheet; (e) Longitudinal section of carbonized corncob after etching; (f-h) SEM images of carbonized corncob after etching; (f) center; (g) sheath; (h) sheet

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图 3 (a) 制备得到的CDs粉末数码照片；(b) 大批量制备的CDs水分散液；(c-d) CDs的TEM照片；(e) 炭化玉米芯尾端(10%)浸在电解液中液体上移的红外照片

Figure 3. (a) Digital picture of CDs powder; (b) Aqueous dispersion of CDs; (c-d) TEM images of CDs; (e) Infrared image of carbonized corncob with tail immersed in electrolyte

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图 4 (a) CDs荧光谱图；(b) CDs和炭化玉米芯(800°C)的XRD谱图；(c) CDs和炭化玉米芯(800 °C)的FTIR光谱图；(d) CDs和炭化玉米芯(800 °C)的XPS谱图；(e) CDs的C1s XPS谱图；(f)炭化玉米芯(800 °C)的C1s XPS谱图

Figure 4. (a) Fluorescence spectra of CDs; (b) XRD patterns of CDs and CC-800; (c) FTIR spectra of CDs and CC-800; (d) XPS survey spectra of CDs and CC-800; (e) XPS survey spectra of C1s for CDs; (f) XPS survey spectra of C1s for CC-800

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图 5 (a) 不同电解液中CDs制备速率图；(b) 不同炭化温度玉米芯电化学制备CDs电压-时间曲线；(c) 不同炭化温度玉米芯XRD谱图；(d-g) 不同炭化温度玉米芯制备CDs 的TEM图：(d) 700 °C，(e) 800 °C，(f) 900 °C，(g) 1000 °C；(h-k) 不同炭化温度玉米芯制备的CDs尺寸统计图：(h) 700 °C，(i) 800 °C，(j) 900 °C，(k) 1000 °C

Figure 5. (a) Preparation rates of CDs with different electrolytes; (b) Volt-time curve of electrochemical preparation of CDs from CC-T; (c) XRD patterns of CC-T; TEM images of CDs from CC-T: (d) 700 °C, (e) 800 °C, (f) 900 °C, (g) 1000 °C; (h-k) CDs size statistics from CC-T: (h) 700 °C, (i) 800 °C, (j) 900 °C, (k) 1000 °C

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图 6 (a) 不同含量CDs的CDs/rGO复合气凝胶数码照片；(b) rGO的TEM、(c) CDs/rGO-4的TEM照片

Figure 6. (a) Digital photos of CDs/rGO aerogel with different contents of CDs; TEM image of (b) rGO and (c) CDs/rGO-4

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图 7 (a) CDs/rGO-4-H的CV曲线；(b) CDs/rGO-4-H的充放电曲线；(c) 不同CDs与rGO复合比例材料的倍率性能图；(d) 不同CDs与rGO复合比例材料的交流阻抗图；(e) CDs/rGO-4-H在1 A g⁻¹下循环性能图

Figure 7. (a) CV curves of CDs/rGO-4-H; (b) the charge-discharge curves of CDs/rGO-4-H; (c) Ratio performance of materials with different CDs and rGO composite ratio; (d) Nyquist impedance plot of materials with different CDs and rGO composite ratios; (e) Cyclic performance of CDs/rGO-4-H at 1 A g⁻¹

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表 1 本研究结果与报道的石墨烯基钠离子电池负极材料性能比较

Table 1. Comparison of the results in this study with reported performance of the graphenebased cathode materials for sodium-ion batteries

Sample	Rate capability (mAh g⁻¹)/ current density (A g⁻¹)	Cyclic stability (mAh g⁻¹)/ current density (A g⁻¹)	Ref.
CDs/rGO aerogel	359.0 / 0.1 268.0 / 5	263.3 / 1 after 1000 cycles	This work
Expanded graphite	284 / 0.02 91 / 0.2	136 / 0.1 after 2000 cycles	[31]
Graphene oxide nanosheets	220 / 0.03 105 / 5	150 / 0.1 after 300 cycles	[32]
Reduced graphene oxide	509 / 0.1 196 / 5	250 / 1 after 1000 cycles	[30]
Graphene oxide paper	290.5 / 0.05 22.4 / 2	210 / 1 after 250 cycles	[33]
Crumpled graphene paper	183 / 0.1 61 / 8	120 / 1 after 500 cycles	[34]
N-carbon dots pillared graphene blocks	520 / 0.02 118 / 10	125 / 10 after 10000 cycles	[13]
3D interconnected hollow channel reduced graphene oxide	329.8 / 0.1 163.9 / 2	166.8 / 1 after 1000 cycles	[35]
Holey graphene oxide	365 / 0.1 131 / 10	163 / 2 after 3000 cycles	[36]
Nitrogen-rich graphene hollow microspheres	253.8 / 0.1 66.7 / 20	77.8 / 10 after 8000 cycles	[37]
Nitrogen-doped graphene foams	1057.1 / 0.1 137.7 / 5	594 / 0.5 after 500 cycles	[38]
Graphene nanowires anchored to 3D graphene foam	497 / 0.0375 203 / 7.5	291 / 0.375 after 1000 cycles	[39]

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