高导电性生物质碳布的制备及其燃料电池气体扩散层性能

doi:10.15541/jim20230127

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1316-1322.DOI: 10.15541/jim20230127 CSTR: 32189.14.10.15541/jim20230127

高导电性生物质碳布的制备及其燃料电池气体扩散层性能

田煜彬¹(), 田超凡¹, 李森¹, 赵永鑫¹, 邢涛², 李智²^,³, 陈萧如¹, 向帅蓉¹, 代鹏程¹()

1.中国石油大学(华东) 新能源学院, 青岛266580
2.山东能源集团有限公司新能源事业部, 济宁 273500
3.西安交通大学材料科学与工程学院, 西安 710049

收稿日期:2023-03-13 修回日期:2023-05-28 出版日期:2023-06-16 网络出版日期:2023-06-16
通讯作者: 代鹏程(1986-), 男, 副教授. E-mail: dpcapple@upc.edu.cn
作者简介:田煜彬(1997-), 男, 硕士研究生. E-mail: yubinpeach@163.com
基金资助:
国家自然科学基金(51702365);山东省自然科学基金(ZR2022MB133)

Biomass-derived High-conductivity Carbon Cloth: Preparation and Application as Gas Diffusion Layers in Fuel Cells

TIAN Yubin¹(), TIAN Chaofan¹, LI Sen¹, ZHAO Yongxin¹, XING Tao², LI Zhi²^,³, CHEN Xiaoru¹, XIANG Shuairong¹, DAI Pengcheng¹()

1. College of New Energy, China University of Petroleum (East China), Qingdao 266580, China
2. New Energy Division, Shandong Energy Group Co., Ltd., Jining 273500, China
3. School of Materials Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Received:2023-03-13 Revised:2023-05-28 Published:2023-06-16 Online:2023-06-16
Contact: DAI Pengcheng (1986-), male, associate professor. E-mail: dpcapple@upc.edu.cn
About author:TIAN Yubin (1997-), male, Master candidate. E-mail: yubinpeach@163.com
Supported by:
National Natural Science Foundation of China(51702365);Natural Science Foundation of Shandong Province(ZR2022MB133)

摘要/Abstract

摘要：

气体扩散层(GDL)是质子交换膜燃料电池(PEMFCs)的关键部件之一, 成本占燃料电池膜电极的40%~50%。开发低成本、高性能的GDL生产工艺, 可以降低燃料电池成本, 推动燃料电池商业化进程。本研究以纤维素棉布为原料, 通过铁基化合物的催化石墨化作用, 在较低温度(1500 ℃)下生成了一种高导电、高孔隙率的柔性生物质碳布。碳布由相互连接的微米级碳纤维组成, 形成了丰富的孔道, 其孔隙率为76.93%。经过铁基化合物催化, 碳纤维的表面原位生成了大量碳纳米管团簇, 增加了碳布的导电性, 使其平面电阻率降低至34 mΩ·cm, 垂直电阻率在 2 MPa压力下降低至2.8 mΩ·cm, 性能达到商业碳布的标准。生物质碳布作为气体扩散层的燃料电池在0.7 A·cm^-2电流密度处功率密度达到0.4 W·cm^-2, 超过了相同催化剂(Pt)负载量的商业碳布(0.34 W·cm^-2)的电池功率密度。本研究制备的生物质碳布制备简单、价格低廉、性能优秀, 为开发低成本、高性能气体扩散层提供了新的思路。

关键词: 生物质, 碳布, 碳纳米管, 气体扩散层, 燃料电池

Abstract:

The gas diffusion layer (GDL) is a critical component of proton exchange membrane fuel cells (PEMFCs) and accounts for 40%-50% of the fuel cell membrane's cost. Developing a low-cost and high-performance GDL is imperative to advance the commercialization of PEMFCs. In this study, we generated a flexible carbon cloth with high electrical conductivity and porosity from cellulose cloth at a low temperature (1500 ℃). The carbon cloth is composed of micron-sized carbon fibers with a porosity of up to 76.93%. Through catalytic graphitization of iron-based compounds, massive carbon nanotube clusters were formed in situ on the surface of carbon fibers, which effectively enhanced the electrical conductivity of the carbon cloth. The in-plane resistance was as low as 34 mΩ·cm while the through-plane resistance was 2.8 mΩ·cm under a pressure of 2 MPa, meeting the performance standard of commercial carbon cloth. Furthermore, the PEMFC with the prepared carbon cloth as GDLs exhibits a power density of 0.4 W·cm^-2 at current density of 0.7 A·cm^-2, exceeding the device with commercial carbon cloth (0.34 W·cm^-2 at 0.7 A·cm^-2). This study demonstrates that the prepared biomass-derived carbon cloth with low-cost and high- performance holds great potential for advanced GDLs for PEMFCs.

Key words: biomass, carbon cloth, carbon nanotube, gas diffusion layer, fuel cell

中图分类号:

TQ174

田煜彬, 田超凡, 李森, 赵永鑫, 邢涛, 李智, 陈萧如, 向帅蓉, 代鹏程. 高导电性生物质碳布的制备及其燃料电池气体扩散层性能[J]. 无机材料学报, 2023, 38(11): 1316-1322.

TIAN Yubin, TIAN Chaofan, LI Sen, ZHAO Yongxin, XING Tao, LI Zhi, CHEN Xiaoru, XIANG Shuairong, DAI Pengcheng. Biomass-derived High-conductivity Carbon Cloth: Preparation and Application as Gas Diffusion Layers in Fuel Cells[J]. Journal of Inorganic Materials, 2023, 38(11): 1316-1322.

图/表 17

图1 生物质碳布的制备流程图

Fig. 1 Preparation procedure of biomass-derived carbon cloth

图2 生物质碳布的XRD谱图(a), Raman谱图(b)和微观制备流程图(c)

Fig. 2 XRD patterns (a), Raman patterns (b) and microcosmic preparative process (c) of biomass-derived carbon cloth

图3 CC-1500的横截面(a), 表面(b)和放大(c)的SEM照片, 以及TEM照片(d)

Fig. 3 SEM images of cross-section (a), surface (b), magnified (c) and TEM (d) image of CC-1500

图4 CC-1500的XPS全谱图(a), C1s(b)、N1s(c)和Fe2p(d) XPS精细图谱

Fig. 4 Survey (a), C1s (b), N1s (c), and Fe2p (d) XPS spectra of CC-1500

图5 不同GDL的平面电阻率(a)和垂直电阻率随压力变化的曲线(b)

Fig. 5 In-plane resistance (a) and through-plane resistance varied with relative pressure (b) of different GDLs

图6 CC-1500和CC-CE的孔径分布图

Fig. 6 Pore size distributions of CC-1500 and CC-CE

图7 不同GDL的极化曲线(a), 功率密度曲线(b), 65 ℃、0.6 V下的阻抗曲线(c)和耐腐蚀曲线(d)

Fig. 7 Polarization curves (a) and power density curves (b), EIS plots (c), and long-term durability tests at 0.6 V, 65 ℃(d) of PEMFCs using different GDLs C: Capacitor; Q: Inductor

图S1 单电池性能测试示意图

Fig. S1 Diagram of single battery performance test

图S2 不同倍率的CC-1000的横截面SEM照片

Fig. S2 Cross-section SEM images of CC-1000 with different magnifications

图S3 不同倍率的CC-N的SEM照片

Fig. S3 SEM images of CC-N with different magnifications

图S4 CC-1000的TEM(a)和HRTEM(b)照片

Fig. S4 TEM (a) and HRTEM(b) images of CC-1000

图S5 CC-1500的TEM(a)和HRTEM(b)照片

Fig. S5 TEM (a) and HRTEM(b) images of CC-1500

图S6 CC-1500的EDS元素分布图

Fig. S6 EDS element mappings of CC-1500

图S7 CC-1000的XPS全谱图(a), C1s(b)、N1s(c)和Fe2p(d) XPS精细图谱

Fig. S7 Survey (a), C1s (b), N1s (c) and Fe2p XPS spectra (d) of CC-1000

图S8 CC-1500的形貌照片(a)和折叠后的照片(b~d)

Fig. S8 Full surface picture (a) and the folded pictures of CC-1500 (b-d)

图S9 不同GDL在55和75 ℃的极化曲线(a, c), 功率密度曲线(b, d)

Fig. S9 Polarization curves(a, c) and power density curves (b, d) of PEMFCs using different GDLs at 55 and 75 ℃

表S1 CC-1500、CC-CE和CC-N的EIS拟合数据

Table S1 EIS fitting data of CC-1500, CC-CE and CC-N

GDL	R_Ω/Ω	R_ct,A/Ω	R_ct,C/Ω
CC-1500	0.3123	0.0832	0.1047
CC-CE	0.3301	0.0658	0.1322
CC-N	0.3442	0.1081	0.1659

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高导电性生物质碳布的制备及其燃料电池气体扩散层性能

Biomass-derived High-conductivity Carbon Cloth: Preparation and Application as Gas Diffusion Layers in Fuel Cells

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