Effect of Pt supported on the hybrid of porous carbon nanofibers and carbon black on oxygen reduction reaction activity and durability
-
摘要: 进一步提高Pt催化剂对氧还原反应(ORR)的催化活性和稳定性是促进质子交换膜燃料电池(PEMFC)商业化的关键。采用静电纺丝结合高温碳化的方法制备了直径约200 nm的多孔纳米碳纤维(PCNF)，将其与炭黑(CB)混合作为Pt催化剂的复合载体，并使用乙二醇还原法制备了催化剂Pt/PCNF-CB，通过与商业Pt/C催化剂的对比，研究了Pt/PCNF-CB对ORR的催化活性与稳定性。当载体中CB含量为40%时，PCNF与CB能相互分散均匀，构建独特的三维贯通结构，以此混合载体制备的催化剂Pt/PCNF-CB-40在酸性电解液中表现出优良的ORR电催化活性，与Pt/C相比具有更高的起始电位(0.975 V)与半波电位(0.781 V)。同时，基于Pt/PCNF-CB-40的膜电极(MEA)表现出优良的输出性能，在铂载量较低的条件下其峰值功率密度高达599 mW·cm−2，较商业Pt/C催化剂提升19%，并且在加速应力测试(AST) (0.6 V和0.95 V)30 k次循环后最大功率密度仅损失21%，而商业Pt/C催化剂损失了41%，证明了PCNF与CB形成的复合载体对提高催化剂活性和稳定性具有积极作用。Abstract: Further improving the activity and stability of Pt catalysts for oxygen reduction reaction (ORR) is the key to promote the commercialization of proton exchange membrane fuel cells (PEMFCs). In this paper, porous carbon nanofibers (PCNF) with a diameter of about 200 nm were prepared by electrospinning and followed carbonization, which were mixed with carbon black (CB) as a hybrid support for Pt catalysts, and the catalysts Pt/PCNF-CB were prepared by means of ethylene glycol reduction method. The electrocatalytic activity and stability of Pt/PCNF-CB for ORR was investigated by comparing it with commercial Pt/C. When the CB content in the support was 40%, PCNF and CB could disperse uniformly to construct a unique three-dimensional through structure, and the Pt/PCNF-CB-40 prepared from this hybrid support shows excellent ORR electrocatalytic activity in acidic electrolyte with higher onset potential (0.975 V) and half-wave potential (0.781 V) compared with commercial Pt/C. Meanwhile, the Pt/PCNF-CB-40-based membrane electrode assembly (MEA) exhibits higher output performance with a peak power density of up to 599 mW·cm−2 at low Pt loading, which is a 19% improvement over the commercial Pt/C, and the maximum power density is only lost by 21% after 30 k of accelerated stress test (AST) (0.6 V-0.95 V), compared with the loss of the commercial Pt/C by 41%, demonstrating that the hybrid support formed by PCNF and CB has a positive effect on improving electrocatalytic activity and stability.
-
图 1 多孔纳米碳纤维(PCNF)制备工艺示意图(a)与PCNF的SEM图像：断面(b)，表面(c)
Figure 1. Process schematic of porous carbon nanofibers (PCNF) (a) and SEM images of PCNF: cross section (b), surface (c)
图 2 催化剂的SEM图像：Pt/PCNF(a)，Pt/PCNF-CB-30(b)，Pt/PCNF-CB-40(c)，Pt/PCNF-CB-50(d)与催化剂的TEM图像：Pt/PCNF(e)，Pt/PCNF-CB-30(f)，Pt/PCNF-CB-40(g)，Pt/PCNF-CB-50(h)
Figure 2. SEM images of electrocatalysts: Pt/PCNF (a), Pt/PCNF-CB-30 (b), Pt/PCNF-CB-40 (c), Pt/PCNF-CB-50 (d) and TEM images of electrocatalysts: Pt/PCNF (e), Pt/PCNF-CB-30 (f), Pt/PCNF-CB-40 (g)，Pt/PCNF-CB-50 (h)
图 5 商业Pt/C与Pt/PCNF-CB在0.5 mol·L−1 H2SO4中的CV曲线，扫描速率为50 mV·s−1(a)以及LSV曲线，扫速为1600 rpm(b)与Tafel斜率(c)
Figure 5. CV curves of commercial Pt/C and Pt/PCNF-CB series electrocatalysts in 0.5 mol·L−1 H2SO4 under the scanning rate of 50 mV·s−1 (a) and LSV curves of commercial Pt/C and Pt/PCNF-CB series electrocatalysts under the 1600 rpm electrode rotation speed (b) and Tafel plots (c)
图 6 商业Pt/C和Pt/PCNF-CB-40催化剂2000圈循环老化前后的CV与LSV曲线
Figure 6. CV and LSV curves of commercial Pt/C and Pt/PCNF-CB-40 electrocatalysts before and after 2000 potential sweeps
图 7 Pt/PCNF-CB-40(a)和商用Pt/C(b)催化剂2000圈循环老化后的TEM图
Figure 7. TEM images of Pt/PCNF-CB-40 (a) and commercial Pt/C (b) electrocatalysts after 2000 potential sweep
图 8 Pt/PCNF-CB-40与Pt/C分别作为阴极的膜电极(MEA)在H2/Air中的极化曲线与功率密度曲线(a)以及Pt/PCNF-CB-40与Pt/C在0.4 A·cm−2下的电化学阻抗谱(EIS)曲线(b)
Figure 8. Polarization and power density curves (a) and electrochemical impedance spectroscopy (EIS) curves (b) of membrane electrode assembly (MEA) of Pt/PCNF-CB-40 and Pt/C as cathodes respectively in H2/Air at 0.4 A·cm−2
图 9 自制催化剂Pt/PCNF-CB-40与商业Pt/C制备的MEA在AST前后的极化曲线和功率密度曲线
Figure 9. Polarization and power density curves of MEA prepared by homemade electrocatalyst Pt/PCNF-CB-40 and commercial Pt/C before and after AST
表 1 以Pt/PCNF-CB-40与Pt/C制备的MEA电化学性能
Table 1. Comparison of electrochemical properties of MEA prepared with Pt/PCNF-CB-40 and Pt/C
Sample The maximum power density/(mW·cm−2) R0/(mΩ·cm−2) Rct/(mΩ·cm−2) Rmt/(mΩ·cm−2) Pt/PCNF-CB-40 599 0.934 4.078 6.565 Pt/C 502 1.815 10.632 8.005 Notes：R0 is the internal resistance of cell including the resistance of each component in cells and their interfaces; Rct is the charge transfer resistance; Rmt is the mass transport resistance. 
下载: 导出CSV
-
[1] LIU Y, YUE X, LI K, et al. PEM fuel cell electrocatalysts based on transition metal macrocyclic compounds[J]. Coordination Chemistry Reviews, 2016, 315: 153-177. doi: 10.1016/j.ccr.2016.02.002 [2] CANO Z P, BANHAM D, YE S, et al. Batteries and fuel cells for emerging electric vehicle markets[J]. Nature Energy, 2018, 3(4): 279-289. doi: 10.1038/s41560-018-0108-1 [3] ZHANG L, ZHANG J, WILKINSON D P, et al. Progress in preparation of non-noble electrocatalysts for PEM fuel cell reactions[J]. Journal of Power Sources, 2006, 156(2): 171-182. doi: 10.1016/j.jpowsour.2005.05.069 [4] ANDÚJAR J M, SEGURA F. Fuel cells: History and updating. a walk along two centuries[J]. Renewable and Sustainable Energy Reviews, 2009, 13(9): 2309-2322. doi: 10.1016/j.rser.2009.03.015 [5] YUSOFF Y N, SHAARI N. An overview on the development of nanofiber-based as polymer electrolyte membrane and electrocatalyst in fuel cell application[J]. International Journal of Energy Research, 2021, 45(13): 18441-18472. doi: 10.1002/er.7020 [6] LIU M, ZHAO Z, DUAN X, et al. Nanoscale structure design for high-performance pt-based ORR catalysts[J]. Advanced Materials, 2019, 31(6): 1802234. doi: 10.1002/adma.201802234 [7] LAMIBRAC A, MARANZANA G, LOTTIN O, et al. Experimental characterization of internal currents during the start-up of a proton exchange membrane fuel cell[J]. Journal of Power Sources, 2011, 196(22): 9451-9458. doi: 10.1016/j.jpowsour.2011.07.013 [8] PARRONDO J, HAN T, NIANGAR E, et al. Platinum supported on titanium–ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles[J]. Proceedings of the National Academy of Sciences, 2014, 111(1): 45-50. doi: 10.1073/pnas.1319663111 [9] MENG Q H, HAO C, YAN B, et al. High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer[J]. Journal of Energy Chemistry, 2022, 71: 497-506. doi: 10.1016/j.jechem.2022.03.018 [10] WANG X, LI Q, PAN H, et al. Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction[J]. Nanoscale, 2015, 7(47): 20290-20298. doi: 10.1039/C5NR05864C [11] LIU J, LIU S, YAN F, et al. Ultrathin nanotube structure for mass-efficient and durable oxygen reduction reaction catalysts in PEM fuel cells[J]. Journal of the American Chemical Society, 2022, 144(41): 19106-19114. doi: 10.1021/jacs.2c08361 [12] HIGGINS D, ZAMANI P, YU A, et al. The application of graphene and its composites in oxygen reduction electrocatalysis: a perspective and review of recent progress[J]. Energy & Environmental Science, 2016, 9(2): 357-390. [13] PUMERA M. Graphene-based nanomaterials and their electrochemistry[J]. Chemical Society Reviews, 2010, 39(11): 4146. doi: 10.1039/c002690p [14] YARAR KAPLAN B, HAGHMORADI N, JAMIL E, et al. Platinum nanoparticles decorated carbon nanofiber hybrids as highly active electrocatalysts for polymer electrolyte membrane fuel cells[J]. International Journal of Energy Research, 2020, 44(13): 10251-10261. doi: 10.1002/er.5646 [15] PARK J H, JU Y W, PARK S H, et al. Effects of electrospun polyacrylonitrile-based carbon nanofibers as catalyst support in PEMFC[J]. Journal of Applied Electrochemistry, 2009, 39(8): 1229-1236. doi: 10.1007/s10800-009-9787-4 [16] Wang M, Xu F, Sun H, et al. Nanoscale graphite-supported Pt catalysts for oxygen reduction reactions in fuel cells[J]. Electrochimica Acta, 2011, 56(5): 2566-2573. doi: 10.1016/j.electacta.2010.11.019 [17] LU L, DENG H, ZHAO Z, et al. N-doped carbon nanotubes supported Pt nanowire catalysts for proton exchange membrane fuel cells[J]. Journal of Power Sources, 2022, 529: 231229. doi: 10.1016/j.jpowsour.2022.231229 [18] KONG J, QIN Y H, WANG T L, et al. Photodeposition of Pt nanoparticles onto TiO2@CNT as high-performance electrocatalyst for oxygen reduction reaction[J]. International Journal of Hydrogen Energy, 2020, 45(3): 1991-1997. doi: 10.1016/j.ijhydene.2019.11.016 [19] HAO C, MENG Q, YAN B, et al. Efficient catalyst layer with ultra-low Pt loading for proton exchange membrane fuel cell[J]. Chemical Engineering Journal, 2023, 472: 144945. doi: 10.1016/j.cej.2023.144945 [20] PARK S, SHAO Y, WAN H, et al. Design of graphene sheets-supported Pt catalyst layer in PEM fuel cells[J]. Electrochemistry Communications, 2011, 13(3): 258-261. doi: 10.1016/j.elecom.2010.12.028 [21] JI Z, CHEN J, PÉREZ-PAGE M, et al. Doped graphene/carbon black hybrid catalyst giving enhanced oxygen reduction reaction activity with high resistance to corrosion in proton exchange membrane fuel cells[J]. Journal of Energy Chemistry, 2022, 68: 143-153. doi: 10.1016/j.jechem.2021.09.031 [22] FU K, WANG Y, MAO L, et al. Facile one-pot synthesis of graphene-porous carbon nanofibers hybrid support for Pt nanoparticles with high activity towards oxygen reduction[J]. Electrochimica Acta, 2016, 215: 427-434. doi: 10.1016/j.electacta.2016.08.111 [23] MAO L, SHAN C, FU K, et al. Porous Carbon Nanofiber/Carbon Black Composite as Promising Support for Platinum Catalyst to Enhance Oxygen Reduction Reaction in PEMFC[J]. ChemistrySelect, 2019, 4(35): 10555-10560. doi: 10.1002/slct.201902857 [24] MAO L, FU K, JIN J, et al. PtFe alloy catalyst supported on porous carbon nanofiber with high activity and durability for oxygen reduction reaction[J]. International Journal of Hydrogen Energy, 2019, 44(33): 18083-18092. doi: 10.1016/j.ijhydene.2019.05.058 [25] ZHOU T, ZHANG J, YANG S, et al. The oxygen reduction performance of pt supported on the hybrid of porous carbon nanofibers and carbon black[J]. Materials, 2022, 15(13): 4560. doi: 10.3390/ma15134560 [26] LI Y, LI Y, ZHU E, et al. Stabilization of high-performance oxygen reduction reaction Pt electrocatalyst supported on reduced graphene oxide/carbon black composite[J]. Journal of American Chemical Society, 2012, 134(30): 12326-12329. doi: 10.1021/ja3031449 [27] TIAN X L, WANG L, CHI B, et al. Formation of a tubular assembly by ultrathin Ti0.8Co0.2N nanosheets as efficient oxygen reduction electrocatalysts for hydrogen-/metal-air fuel cells[J]. ACS Catalysis, 2018, 08(10): 8970-8915. doi: 10.1021/acscatal.8b02710 [28] ZHAO C, LIU J, LI B, et al. Multiscale construction of bifunctional electrocatalysts for long-lifespan rechargeable zinc-air batteries[J]. Advanced Functional Materials, 2020, 30(36): 2003619. doi: 10.1002/adfm.202003619 [29] XIN L, YANG F, RASOULI S, et al. Understanding Pt nanoparticle anchoring on graphene supports through surface functionalization[J]. ACS Catalysis, 2016, 6(4): 2642-2653. doi: 10.1021/acscatal.5b02722 [30] MEIER J C, GALEANO C, KATSOUNAROS I, et al. Degradation mechanisms of Pt/C fuel cell catalysts under simulated start-stop conditions[J]. ACS Catalysis, 2012, 2(5): 832-843. doi: 10.1021/cs300024h [31] TAO L, QIAO M, JIN R, et al. Bridging the surface charge and catalytic activity of a defective carbon electrocatalyst[J]. Angewandte Chemie International Edition, 2019, 58(4): 1019-1024. doi: 10.1002/anie.201810207 [32] CHENG Q, HU C, WANG G, et al. Carbon-defect-driven electroless deposition of pt atomic clusters for highly efficient hydrogen evolution[J]. Journal of the American Chemical Society, 2020, 142(12): 5594-5601. doi: 10.1021/jacs.9b11524 -
下载:
点击查看大图
计量
- 文章访问数: 61
- HTML全文浏览量: 44
- 被引次数: 0
