不同生物质来源的多孔碳复合碳电极在钙钛矿太阳能电池中的应用

刘海潮; 谢亚红; 魏鹏; 耿聪; 王昊斌; 郑申申

doi:10.13801/j.cnki.fhclxb.20211209.001

不同生物质来源的多孔碳复合碳电极在钙钛矿太阳能电池中的应用

doi: 10.13801/j.cnki.fhclxb.20211209.001

新疆大学　化工学院石油天然气精细化工教育部/自治区重点实验室, 新疆 830046

基金项目: 大连理工大学精细化工国家重点实验室开放项目(KF2004)；新疆维吾尔自治区大学科研计划自然科学项目(XJEDU2020I006)；新疆维吾尔自治区重点实验室开放项目(2019D04006)

详细信息

作者简介:
谢亚红，新疆大学教授，博士研究生导师，新疆优秀青年科技人才。博士毕业于日本东北大学，中国科学院新疆理化技术研究所博士后，大连理工大学、加拿大滑铁卢大学访问学者。中国可再生能源学会光化学专业委员会委员。主要研究领域：光电功能材料，光催化材料，新型太阳能电池的开发与低温制备，油田精细化学品。研究包括微/纳米催化/光催化功能材料的合成及其催化性能研究，新型硅基材料、碳材料的合成及其性能研究，染料敏化太阳能电池、钙钛矿薄膜太阳能电池，无机半导体薄膜太阳能关键材料的开发与研究。主持和结题包括国家自然科学基金、自治区自然科学基金、国家博士后基金、自治区重点实验室开放课题在内的课题10多项。在Chem. Mater., Chem. Eng.J., ChemComm, J. Power Sources, Carbon等国际期刊上以第一作者和通讯作者发表学术论文50余篇，获得新疆大学第五届青年科研奖，新疆大学自然科学一等奖（排名第一），新疆维吾尔自治区自然科学二等奖（排名第一）

通讯作者:
谢亚红，博士，教授，硕士生/博士生导师，研究方向为光电转化与储存材料的设计合成与综合利用　E-mail: xyh0707@163.com

中图分类号: TM914.4
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出版历程
- 收稿日期: 2021-09-06
- 修回日期: 2021-11-16
- 录用日期: 2021-12-13
- 网络出版日期: 2021-12-13
- 刊出日期: 2022-03-23

Application of porous carbon composite carbon electrodes from different biomass sources in perovskite solar cells

Key Laboratory of Oil & Gas Fine Chemicals, Ministry of Education and Xinjiang Uyghur Autonomous Region, College of Chemistry and Chemical Engineering, Xinjiang University, Xinjiang 830046, China

摘要

摘要: 通过将生物质在惰性气体保护下高温热解/活化制备多孔碳材料，具有成本低，工艺简单等优点，并且是一种废物利用，减少环境污染的有效途径。将三种不同生物质通过高温热解/活化制备了多孔碳材料，将其与市售导电碳浆复合制成碳浆料后应用于钙钛矿太阳能电池(PSCs)背电极，研究了不同生物质多孔碳材料的形貌、结构和比表面积等对器件光电性能的影响。结果表明，基于不同生物质多孔碳材料的PSCs的光电性能取决于生物质多孔碳材料的形貌、结晶度、比表面积和形态以及钙钛矿/碳电极的界面接触。基于生物质多孔碳的复合碳电极结合研磨工艺制备的碳基PSCs，由于具有良好的界面性能获得最高10.18％的光电转换效率(PCE)(未复合生物质碳的PSCs的PCE为6.39%)，室温下保存60天后，仍保留了初始PCE的96％。
- 生物质 /
- 高温活化/热解 /
- 生物质多孔碳的复合碳电极 /
- 钙钛矿太阳能电池 /
- 界面特性
Abstract: The preparation of porous carbon materials by high-temperature pyrolysis/activation of biomass under the protection of inert gas has the advantages of low cost, simple process, etc., and is an effective way to use waste and reduce environmental pollution. In this study, three different biomass materials were prepared by high-tempe-rature pyrolysis/activation to prepare porous carbon materials, which were combined with commercially conduc-tive carbon paste to make composite carbon paste and applied to the counter electrodes of perovskite solar cells (PSCs). The morphology, structure and specific surface area of different biomass porous carbon materials affect the photoelectric performance of the device. The results show that the photoelectric performance of PSCs based on different biomass porous carbon materials depends on the morphology, crystallinity, specific surface area and morphology of the biomass porous carbon materials and the interface contact between the perovskite/carbon electrode. The carbon-based PSCs prepared by the composite carbon electrode based on biomass porous carbon combined with the grinding process can obtain the highest photoelectric conversion efficiency (PCE) of 10.18% due to its good interface performance (the PCE of the PSCs without composite biomass carbon is 6.39%). After the best device is stored in air conditions for 60 days, 96% of the initial PCE was still retained.
- biomass /
- high-temperature activation/pyrolysis /
- composite carbon electrode of biomass porous carbon /
- perovskite solar cells /
- interface characteristics

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图 1 700℃热解/活化后CSC、COC和SDC的SEM图像

Figure 1. SEM images of CSC, COC and SDC after 700℃ pyrolysis/activation

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图 2 CSC、COC和SDC的XRD图谱(a)、Raman图谱(b)、氮气吸脱附等温线(c)和孔径分布曲线(d)

Figure 2. XRD spectra (a), Raman spectra (b), nitrogen adsorption and desorption isotherms (c) and pore size distribution curves (d) of CSC, COC and SDC

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图 3 (a) 钙钛矿太阳能电池的截面SEM图像; (b) 钙钛矿太阳能电池的结构示意图

Figure 3. (a) Cross-sectional SEM image of PSCs; (b) Schematic diagram of the structure of PSCs

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图 4 SDC、COC、CSC和CPC器件的J-V曲线(a)、阻抗谱图和等效电路图(b)

Figure 4. J-V curves (a) and impedance spectrogram and equivalent circuit diagrams (b) of SDC, COC, CSC and CPC devices

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图 5 (a) SDC、COC、CSC和CPC器件在经过20 s光照后的延迟开路光电压降(OCVD)；(b) OCVD曲线对应的依据电子空穴复合机制得到的电子寿命τ'_n和开路电压V_oc的关系图

Figure 5. (a) Delayed open circuit photovoltage drop (OCVD) of SDC, COC, CSC and CPC device after 20 seconds illumination; (b) Relationship between the electron lifetime τ'_n and the open circuit voltage V_oc obtained by the electron hole recombination mechanism corresponding to the OCVD curve

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图 6 用光电参数显示的SDC、COC、CSC和CPC器件的箱形图

Figure 6. Statistical box diagrams of SDC, COC, CSC and CPC device

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图 7 SDC、COC、CSC和CPC器件的正反扫曲线

Figure 7. Reverse and forward scan curves of SDC, COC, CSC and CPC device

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图 8 SDC (a)、COC (b)、CSC (c)和CPC (d)基C-PSCs在最大功率点的稳态光电流测试

Figure 8. Steady-state photocurrent output of SDC (a), COC (b), CSC (c) and CPC (d)-based C-PSCs

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图 9 SDC (a)、COC (b)、CSC (c)和CPC (d)基C-PSCs器件在空气条件下60天的稳定性测试

Figure 9. SDC (a), COC (b), CSC (c) and CPC (d)-based C-PSCs stability test under air conditions for 60 days

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表 1 CSC、COC和SDC生物质碳样品BET参数

Table 1. BET parameters of CSC, COC and SDC bio-carbon samples

Sample	SSA /(m²·g⁻¹)	V_total /(cm³·g⁻¹)	V_micro /(cm³·g⁻¹)	V_meso /(cm³·g⁻¹)	D /nm
Sample	SSA /(m²·g⁻¹)	V_total /(cm³·g⁻¹)	V_micro /(cm³·g⁻¹)	V_meso /(cm³·g⁻¹)	D /nm	CSC	1067	0.374	0.314	0.060	1.74
COC	1220	0.396	0.312	0.084	1.79
SDC	1404	0.592	0.434	0.158	1.92
Notes: SSA—Specific surface area; V_total—Total pore volume; V_micro—Micropore volume; V_meso—Mesopore volume; D—Average pore diameter.

下载: 导出CSV

表 2 SDC、COC、CSC和CPC器件的最佳光电性能和平均光电参数

Table 2. Optimal and average optoelectronic parameters of SDC, COC, CSC and CPC device

Sample		V_oc/V	J_sc/(mA·cm⁻²)	FF	PCE/%
SDC	Best	0.87	22.86	0.51	10.18
SDC	Average	0.87±0.02	20.91±0.67	0.48±0.03	9.17±0.58
COC	Best	0.87	21.31	0.49	9.03
COC	Average	0.81±0.06	20.17±1.26	0.44±0.04	7.46±0.99
CSC	Best	0.83	22.40	0.41	7.62
CSC	Average	0.80±0.05	20.97±1.84	0.41±0.02	6.78±0.52
CPC	Best	0.77	20.31	0.41	6.39
CPC	Average	0.75±0.04	17.10±1.49	0.43±0.02	5.48±0.59
Notes: V_oc—Voltage of open circuit; J_sc—Current of short circuit; FF—Fill factor; PCE—Photoelectric conversion efficiency.

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表 3 SDC、COC、CSC和CPC器件的阻抗参数

Table 3. Optical impedance parameters of SDC, COC, CSC and CPC devices

Sample	R_s/Ω	R_tr/Ω	R_rec/Ω
SDC	20.13	69.93	92.96
COC	15.8	70.76	29.75
CSC	18.7	87.13	47.89
CPC	16.5	43.12	66.71
Notes: R_s—Sheet resistance; R_tr—Transfer resistance; R_rec—Recombination resistance.

下载: 导出CSV

表 4 SDC、COC、CSC和CPC器件的正反扫光电性能数据和迟滞因子

Table 4. Reverse and forward scanning photoelectric performance data and hysteresis factor of SDC, COC, CSC and CPC device

Sample	V_oc/V	J_sc/(mA·cm⁻²)	FF	PCE/%	HF/%
SDC-R	0.87	21.49	0.54	10.05	8
SDC-F	0.85	21.88	0.50	9.25	8
COC-R	0.87	19.86	0.52	8.92	14
COC-F	0.85	18.76	0.49	7.71	14
CSC-R	0.81	21.20	0.42	7.18	23
CSC-F	0.73	22.76	0.33	5.53	23
CPC-R	0.75	18.91	0.43	6.10	32
CPC-F	0.66	18.60	0.34	4.15	32
Note: HF—Hysteresis factor.

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