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金刚石/石墨烯复合电极因能发挥金刚石组分的低背景电流和宽电势窗口, 且兼具石墨组分的高电化学活性, 引起了人们的广泛关注. 本文采用热丝化学气相沉积方法, 通过调控短时生长时间, 在纳米金刚石单颗粒层表面的竖立石墨烯片中嵌入纳米金刚石, 形成复合三维电极. 结果表明, 当竖立石墨烯片顶部生长了纳米金刚石时, 电极显示较宽的电势窗口(3.59 V)和极低的背景电流(1.27 mA/cm2), 片层顶部少层石墨包覆纳米金刚石晶粒的复合结构是拓宽电势窗口和降低背景电流的关键. 随着生长时间延长, 竖立片层长大, 纳米金刚石晶粒嵌入到片层中, 构建了新型的纳米金刚石/石墨烯复合竖立片层结构; 有序的石墨结构使得电化学活性面积增大为677.19 μC/cm2和比电容增至627.34 μF/cm2, 石墨组分增多使得电势窗口变窄, 嵌入片层中的纳米金刚石有效地降低背景电流. 本研究提供了一种热丝化学气相沉积方法制备纳米金刚石/石墨烯复合三维电极的新方法, 并为充分发挥金刚石/石墨烯复合薄膜的协同效应提供了一种新思路.Diamond/graphene composite three-dimensional electrode has attracted extensive attention because of its low background current, wide potential window from diamond component, and high electrochemical activity from graphite component. In this work, by using the hot wire chemical vapor deposition method, nano diamonds are embedded in the vertical graphene sheet on the surface of single particle layer of nano diamond by regulating the short-term growth time to form a composite three-dimensional electrode. The results show that the electrode exhibits a wide potential window (3.59 V) and a very low background current (1.27 mA/cm2) when nano-diamond crystals grow on the top of the vertical graphene sheet. The composite structure of nano-diamond crystals coated with graphite on the top of the graphene sheet is the key to broadening the potential window and reducing the background current. With the increase of growth time, the vertical graphene sheet grows and nano-diamond grains are embedded into the lamellae, and a novel nano-diamond/graphene composite vertical lamellae structure is constructed. The ordered graphite structure increases the electrochemical active area to 677.19 μC/cm2 and the specific capacitance to 627.34 μF/cm2. The increase of graphite components makes the potential window narrow, and the embedded nano-diamond crystals effectively reduce the background current. This study provides a new method for preparing three-dimensional nanodiamond/graphene composite electrodes by hot wire chemical vapor deposition, and provides a new idea for fully exploiting the synergistic effect of diamond/graphene composite films.
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Keywords:
- nano-diamond /
- vertical graphene /
- electrode /
- electrochemical properties
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图 1 不同生长时间下复合薄膜的FESEM形貌和截面图, 内插图为对应样品的静态水接触角图 (a), (e), (i) 1.5 min; (b), (f), (j) 2 min; (c), (g), (k) 2.5 min; (d), (h), (l) 3 min
Fig. 1. FESEM images for frontal and cross-sectional morphologies of composite films under different growth times, the inset images show the static water contact angle diagram from the corresponding samples under different growth times: (a), (e), (i) 1.5 min; (b), (f), (j) 2 min; (c), (g), (k) 2.5 min; (d), (h), (l) 3 min.
图 2 (a) 样品在800到2000 cm–1波数的可见光Raman光谱及拟合曲线; (b) 样品在2200到3100 cm–1波数的可见光Raman光谱; (c) 样品的Raman光谱拟合结果演化图
Fig. 2. Visible Raman spectra of the samples at the range of (a) 800–2000 cm–1 and (b) 2200–3100 cm–1. (c) The evolution of several typical parameters from the Raman fitting results.
图 3 不同生长时间样品的低倍, 高倍和对应白框选定区域的放大图, 及其对应区域的FFT图 (a), (e) 1.5 min; (b), (f) 2 min; (c), (g) 2.5 min; (d), (h) 3 min. (e1)—(h1), (e2)—(h2) 图(e)—(h)中对白框选定区域的放大图以及其相应的对应区域的FFT图
Fig. 3. The low- and high-magnificent TEM images with inset corresponding FFTs from samples under different growth times: (a), (e) 1.5 min; (b), (f) 2 min; (c), (g) 2.5 min; (d), (h) 3 min. (e1)–(h1), (e2)–(h2) are enlarged images and corresponding FFTs of the selected areas in the corresponding white boxes in Figure (e)–(h).
图 4 不同生长时间的NDs-VGs-SPL薄膜电极(a)在1 M KCl体系中的电势窗口和背景电流和(b)在 1 mM K3Fe(CN)6+1 M KCl 体系中以 100 mV/s 扫速下的循环伏安图. 图(a)和图(b)插入的表格列出了扫描速度为100 mV/s时的相应参数
Fig. 4. Cyclic voltammetry curves for NDs-VGs-SPL electrodes in 1 M KCl solution (a) and in 1 mM K3Fe(CN)6+ 1 M KCl solution (b). The inset tables are their corresponding parameters under the scanning rate of 100 mV/s.
图 5 不同生长时间下复合薄膜电极在0.1—0.5 V/s扫描速率下1 mol/L KOH体系中的循环伏安曲线 (a) NDs-VGs-SPL-1.5; (b) NDs-VGs-SPL-2; (c) NDs-VGs-SPL-2.5; (d) NDs-VGs-SPL-3
Fig. 5. Cyclic voltammetry curves for NDs-VGs-SPL electrodes of (a) NDs-VGs-SPL-1.5, (b) NDs-VGs-SPL-2, (c) NDs-VGs-SPL-2.5, (d) NDs-VGs-SPL-3 in 1 M KOH solution under the scanning rate of 0.1–0.5 V/s.
图 6 (a) 不同生长时间下复合薄膜电极在100 mV/s扫描速率下循环伏安曲线; (b) 复合薄膜电极对应的电容柱状图
Fig. 6. (a) Cyclic voltammetry curves for NDs-VGs-SPL electrodes in 1 M KOH solution under the scanning rate of 100 mV/s; (b) capacitance histograms corresponding to NDs-VGs-SPL electrodes.
表 1 Raman光谱拟合结果汇总
Table 1. Summary of the data from the fitted Raman spectra.
样品 1332
/arb. unitsD'
/arb. unitsG
/arb. unitsFWHMG
/cm–1D'
/arb. units2D
/arb. unitsITPA/ISUM I2D/IG 1.5 min 0.22 0.58 0.43 90.56 — 0.17 0.44 0.40 2.0 min — 0.84 0.73 44.85 0.26 0.57 0.35 0.65 2.5 min — 0.85 0.48 34.12 0.22 0.31 0.30 0.63 3.0 min — 0.92 0.66 33.40 0.21 0.76 0.28 1.14 注: 表格中“—”符号表示Raman光谱中未检测到此峰位. 
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[1] Lesiak B, Kövér L, Tóth J, Zemek J, Jiricek P, Kromka A, Rangam N 2018 Appl. Surf. Sci. 452 223
Google Scholar
[2] Zhai Z, Huang N, Jiang X 2022 Curr. Opin. Electrochem. 32 100884
Google Scholar
[3] Chen C K, He Z, Xu A, Li X, Jiang M, Xu T, Yan B, Hu X 2021 Funct. Diamond 1 117
Google Scholar
[4] 胡衡, 胡晓君, 白博文, 陈小虎 2012 61 148101
Google Scholar
Hu H, Hu X J, Bai B W, Chen X H 2012 Acta Phys. Sin. 61 148101
Google Scholar
[5] 潘金平, 胡晓君, 陆利平, 印迟 2010 59 7410
Google Scholar
Pan J P, Hu X J, Lu L P, Yin C 2010 Acta Phys. Sin. 59 7410
Google Scholar
[6] 胡晓君, 李荣斌, 沈荷生, 何贤昶, 邓 文, 罗里熊 2004 53 2014
Google Scholar
Hu X J, Li R B, Shen H S, He X C, Deng W, Luo L X 2004 Acta Phys. Sin. 53 2014
Google Scholar
[7] Yang N, Yu S, Macpherson J V, Einaga Y, Zhao H, Zhao G, Swain G M, Jiang X 2019 Chem. Soc. Rev. 48 157
Google Scholar
[8] Gao F, Nebel C E 2016 ACS Appl. Mater. Interfaces 8 28244
Google Scholar
[9] Watanabe T, Honda Y, Kanda K, Einaga Y 2014 Phys. Status Solidi A 211 2709
Google Scholar
[10] Sun Y, Wu Q, Xu Y, Bai H, Li C, Shi G 2011 J. Mater. Chem. 21 7154
Google Scholar
[11] Wei M, Terashima C, Lv M, Fujishima A, Gu Z Z 2009 Chem. Commun. 24 3624
Google Scholar
[12] 蒋梅燕, 朱政杰, 陈成克, 李晓, 胡晓君 2019 68 148101
Google Scholar
Jiang M Y, Zhu Z J, Chen C K, Li X, Hu X J 2019 Acta Phys. Sin. 68 148101
Google Scholar
[13] 王锐, 胡晓君 2014 63 148102
Google Scholar
Wang R, Hu X J 2014 Acta Phys. Sin. 63 148102
Google Scholar
[14] Sobaszek M, Siuzdak K, Ryl J, Sawczak M, Gupta S, Carrizosa S B, Ficek M, Dec B, Darowicki K, Bogdanowicz R 2017 J. Phys. Chem. C 121 20821
Google Scholar
[15] Shen A, Zou Y, Wang Q, Dryfe R A W, Huang X, Dou S, Dai L, Wang S 2014 Angew. Chem. Int. Ed. 53 10804
Google Scholar
[16] Kamata T, Kato D, Ida H, Niwa O 2014 Diamond Relat. Mater. 49 25
Google Scholar
[17] Garcia-Segura S, Vieira dos Santos E, Martínez Huitle C A 2015 Electrochem. Commun. 59 52
Google Scholar
[18] Ayres Z J, Borrill A J, Newland J C, Newton M E, Macpherson Julie. V 2016 Anal. Chem. 88 974
Google Scholar
[19] Cobb S J, Ayres Z J, Macpherson J V 2018 Annu. Rev. Anal. Chem. 11 463
Google Scholar
[20] Vlasov I, Lebedev O I, Ralchenko V G, Goovaerts E, Bertoni G, Van Tendeloo G, Konov V I 2007 Adv. Mater. 19 4058
Google Scholar
[21] Arenal R, Bruno P, Miller D J, Bleuel M, Lal J, Gruen D M 2007 Phys. Rev. B 75 195431
Google Scholar
[22] Sankaran K J, Kurian J, Chen H C, Dong C L, Lee C Y, Tai N H, Lin I N 2012 J. Phys. D:Appl. Phys. 45 365303
Google Scholar
[23] Shang N, Papakonstantinou P, Wang P, Zakharov A, Palnitkar U, Lin I N, Chu M, Stamboulis A 2009 ACS Nano 3 1032
Google Scholar
[24] Shalini J, Sankaran K J, Dong C L, Lee C Y, Tai N H, Lin I N 2013 Nanoscale 5 1159
Google Scholar
[25] Shalini J, Lin Y C, Chang T H, Sankaran K J, Chen H C, Lin I N, Lee C Y, Tai N H 2013 Electrochim. Acta 92 9
Google Scholar
[26] Zhai Z, Huang N, Yang B, Wang C, Liu L, Qiu J, Shi D, Yuan Z, Lu Z, Song H, Zhou M, Chen B, Jiang X 2019 J. Phys. Chem. C 123 6018
Google Scholar
[27] Yu S, Sankaran K J, Korneychuk S, Verbeeck J, Haenen K, Jiang X, Yang N 2019 Nanoscale 11 17939
Google Scholar
[28] 邢丽丹, 谢启明, 李伟善 2020 69 228205
Google Scholar
Xing L D, Xie Q M, Li W S 2020 Acta Phys. Sin. 69 228205
Google Scholar
[29] Wu, Yang 2002 Nano Lett. 2 355
Google Scholar
[30] Tzeng Y, Chen W L, Wu C, Lo J Y, Li C Y 2013 Carbon 53 120
Google Scholar
[31] Banerjee D, Sankaran K J, Deshmukh S, Ficek M, Bhattacharya G, Ryl J, Phase D M, Gupta M, Bogdanowicz R, Lin I N, Kanjilal A, Haenen K, Roy S S 2019 J. Phys. Chem. C 123 15458
Google Scholar
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Google Scholar
[33] Zhou M, Zhai Z, Liu L, Zhang C, Yuan Z, Lu Z, Chen B, Shi D, Yang B, Wei Q, Huang N, Jiang X 2021 Appl. Surf. Sci. 551 149418
Google Scholar
[34] Jiang M Y, Ma W C, Han S J, Chen C K, Fan D, Li X, Hu X J 2020 J. Appl. Phys. 127 015301
Google Scholar
[35] Jiang M Y, Zhang Z Q, Chen C K, Ma W C, Han S J, Li X, Lu S H, Hu X J 2020 Carbon 168 536
Google Scholar
[36] Jiang M Y, Chen C K, Wang P, Guo D F, Han S J, Li X, Lu S H, Hu X J. 2022 PNAS 119 2201451119
Google Scholar
[37] Chen C K, Fan D, Xu H J, Jiang M Y, Li X, Lu S H, Ke C C, Hu X J. 2022 Carbon 196 466
Google Scholar
[38] 胡晓君, 仰宗春 2015 中国专利 ZL 201510149374.4 [2017-04-12]
Hu X J, Yang Z C 2015 Chin. Patent ZL 201510149374.4 [2017-04-12]
[39] Klauser F, Steinmüller Nethl D, Kaindl R, Bertel E, Memmel N 2010 Chem. Vap. Deposition 16 127
Google Scholar
[40] Malard L M, Pimenta M A, Dresselhaus G, Dresselhaus M S 2009 Phys. Rep. 473 51
Google Scholar
[41] Cançado L G, Jorio A, Ferreira E H M, Stavale F, Achete C A, Capaz R B, Moutinho M V O, Lombardo A, Kulmala T S, Ferrari A C 2011 Nano Lett. 11 3190
Google Scholar
[42] Shimada T, Sugai T, Fantini C, Souza M, Cançado L G, Jorio A, Pimenta M A, Saito R, Grüneis A, Dresselhaus G, Dresselhaus M S, Ohno Y, Mizutani T, Shinohara H 2005 Carbon 43 1049
Google Scholar
[43] Ferrari A C, Robertson J. Resonant 2001 Phys. Rev. B 64 075414
Google Scholar
[44] Vora H, Moravec T J 1981 J. Appl. Phys. 52 6151
Google Scholar
[45] Konyashin I, Frost D J, Sidorenko D, Orekhov A, Obraztsova E A, Sviridova T A 2020 Diamond Relat. Mater. 109 108017
Google Scholar
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