Study on performance of polyethersulfone-polyvinylpyrrolidone high temperature polymer electrolyte membrane and fuel cell stack

doi:10.11949/0438-1157.20200962

Abstract

Abstract:

High temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) based on phosphoric acid doped polybenzimidazole (PA/PBI) membrane express high stability and outstanding performance. However, the high price and complex fabrication procedures of PBI substantially hinder the commercial application of PBI in HT-PEMFCs. This study aims to accelerate the commercial application of polyether sulfone-polyvinyl pyrrolidone (PES-PVP) membrane in HT-PEMFCs. The achievement of PES-PVP membrane with width of 40 cm proves feasibility for scale-up production of the PES-PVP membrane. After PA doping, the membrane obtains PA uptake of 4.9 PA per repeat unit of PVP and the high proton conductivity of 85 mS·cm^-1 at 180℃. In addition, the PA/PES-PVP membrane fuel cell with active area of 165 cm² shows power output of 0.19 W·cm^-2@0.6 V at 150℃ under H₂/air atmosphere. That is comparative to the power output of commercial PA/PBI membrane fuel cells under the same test conditions. Furthermore, the fuel cell shows exceptional durability up to 3000 h under 150℃. In addition, the fuel cell stack containing 3 cells with active area of 200 cm² shows outstanding stability during start-up/shut down cycles, while the fuel cell stack with 20 cells shows peak power output of 1.15 kW under the same test conditions. Overall, the PA/PES-PVP composite membranes with low cost show excellent performance in HT-PEMFCs, which have promising application for the commercialization of domestic HT-PEMFCs. This research work provides a research foundation for the localization of key materials and stacks for high-temperature polymer electrolyte membrane fuel cells.

Key words: high temperature polymer electrolyte membrane, PES-PVP, electrochemistry, fuel cells, stability

摘要：

基于磷酸掺杂聚苯并咪唑膜（PA/PBI）的高温聚合物电解质膜燃料电池具有高的输出功率和优异的稳定性，然而PBI膜昂贵的价格和复杂的制备工艺限制了高温聚合物电解质膜燃料电池的商业化应用。本研究以成本低和制备工艺简单的聚醚砜-聚乙烯吡咯烷酮（PES-PVP）膜的商业化应用为目标，小规模制备了幅宽为40 cm的PES-PVP复合膜，证实了流延法放大制备PES-PVP复合膜的可行性。PES-PVP膜中每个PVP重复单元的吸附量达4.9个磷酸（PA）分子，且在180℃的质子电导率达85 mS·cm^-1。此外，尺寸为165 cm²的PA/PES-PVP高温膜电极在150℃的输出功率达0.19 W·cm^-2@0.6 V，与同尺寸的商业化PA/PBI高温膜电极的输出功率相当，并在近3000 h的寿命测试中展示出良好的稳定性。最后，将PA/PES-PVP高温膜电极（单片有效面积200 cm²）组装高温膜燃料电池短堆，其中基于3片膜电极的短堆展现出良好的电堆启停稳定性；基于20片膜电极电堆的峰值功率达1.15 kW。以上结果表明所制备的PA/PES-PVP是一种性能优良、价格便宜的高温聚合物电解质膜材料，并且基于该膜材料组装的高温聚合物电解质膜电池和电堆性能优异。本研究工作为高温聚合物电解质膜燃料电池关键材料和电堆的国产化提供了研究基础。

关键词: 高温聚合物电解质膜, 聚醚砜-聚乙烯吡咯烷酮, 电化学, 燃料电池, 稳定性

CLC Number:

TM 911.4

ZHANG Jin, GUO Zhibin, ZHANG Jujia, WANG Haining, XIANG Yan, JIANG San Ping, LU Shanfu. Study on performance of polyethersulfone-polyvinylpyrrolidone high temperature polymer electrolyte membrane and fuel cell stack[J]. CIESC Journal, 2021, 72(1): 589-596.

张劲, 郭志斌, 张巨佳, 王海宁, 相艳, 蒋三平, 卢善富. 聚醚砜-聚乙烯吡咯烷酮高温聚合物电解质膜及燃料电池堆性能研究[J]. 化工学报, 2021, 72(1): 589-596.

Figures/Tables 5

Fig.1 Picture of scale-up fabrication of PES-PVP composite membrane via casting method, and the width of the membrane is 40 cm(a); the stress-strain curves of the PES-PVP composite membrane and PBI membrane before and after PA uptake (b); the PA uptake level and volume swelling ratio of PA saturated PES-PVP and PBI membranes (c); the proton conductivity of PA/PES-PVP composite membrane and PA/PBI membrane under different temperature and unhydrous conditions (d)

Fig.2 The optical pictures of MEAs based on the PA/PES-PVP membrane with different active size

Fig.3 Polarization curves of PA/PES-PVP membrane fuel cell with active area of 200 cm2 at 150℃ under H2/O2 with stoichiometry ratio of 3 and 9, respectively, without backpressure (a); cell performance comparison among PA/PES-PVP MEA (BUAA HT-MEA) and two commercial HT-PEM MEAs (Advent and DPS) with active area of 165 cm2 under 150℃ and the stoichiometry ratio of H2 and air is 2 and 5, respectively, without backpressure (b)

Fig.4 The durability test of PA/PES-PVP membrane fuel cell with a constant load of 200 mA·cm-2 at 150℃, the stiochimitry of H2 and air is 3 and 6，respectively, without backpressure

Fig.5 Bipolar plate of anode and cathode (a), liquid cooling channel [(b),(c)]; picture of the fuel cell stack test (d); stability of fuel cell stack with 3 MEAs (e); stack performance with 20 MEAs (f)(testing conditions: active area 200 cm2, anode H2, cathode air，λH2=3, λair=9 without backpressure; temperature is 150℃)

References 31

1	王诚, 王树博, 张剑波, 等. 车用质子交换膜燃料电池材料部件[J]. 化学进展, 2015, 27(2/3): 310-320.
	Wang C, Wang S B, Zhang J B, et al. The key materials and components for proton exchange membrane fuel cells[J]. Progress in Chemistry, 2015, 27(2/3): 310-320.
2	Liang Y, Zhang H, Zhang J, et al. Porous 2D carbon nanosheets synthesized via organic groups triggered polymer particles exfoliation: an effective cathode catalyst for polymer electrolyte membrane fuel cells[J]. Electrochimica Acta, 2020, 332: 135397.
3	万忠民, 全文祥, 阎瀚章, 等. 无人机用燃料电池系统性能分析[J]. 化工学报, 2019, 70: 329-335.
	Wan Z M, Quan W X, Yan H Z, et al. Performance analysis of fuel cell system for unmanned aerial vehicle [J]. CIESC Journal, 2019, 70: 329-335.
4	Zhang J, Liu J, Lu S, et al. Ion-exchange-induced selective etching for the synthesis of amino-functionalized hollow mesoporous silica for elevated-high-temperature fuel cells[J]. ACS Applied Materials & Interfaces, 2017, 9: 31922-31930.
5	李庆, 叶强, 杨晓光. 电解重整式甲醇燃料电池系统[J]. 化工学报, 2013, 64(4): 1373-1379.
	Li Q, Ye Q, Yang X G. PEMFC system incorporating a methanol electrolytic reformer[J]. CIESC Journal, 2013, 64(4): 1373-1379.
6	Wang S, Jiang S P. Prospects of fuel cell technologies[J]. National Science Review, 2017, 4(2): 163-166.
7	Cheng Y, Zhang J, Lu S F, et al. Significantly enhanced performance of direct methanol fuel cells at elevated temperatures[J]. Journal of Power Sources, 2020, 450: 227620.
8	李微微, 尚玉明, 王树博, 等. AB-PBI分子量对高温膜燃料电池膜电极性能的影响[J]. 化工学报, 2011, 62(2): 131-134.
	Li W W, Shang Y M, Wang S B, et al. Effect of polymer molecular weight of ABPBI on membrane electrode assembly of high temperature proton exchange membrane fuel cells[J]. CIESC Journal, 2011, 62(2): 131-134.
9	Huang Y J, Li Q F, Anfimova T V, et al. Indium doped niobium phosphates as intermediate temperature proton conductors[J]. International Journal Hydrogen Energy, 2013, 38(5): 2464-2470.
10	卢善富, 徐鑫, 张劲, 等. 燃料电池用磷酸掺杂高温质子交换膜研究进展[J]. 中国科学: 化学, 2017, 47(5): 565-572.
	Lu S F, Xu X, Zhang J, et al. Progress of phosphoric acid doped high temperature proton exchange membrane for fuel cells[J]. Scientia Sinica Chimica, 2017, 47(5): 565-572.
11	Zhang J, Aili D, Lu S F, et al. Advancement toward polymer electrolyte membrane fuel cells at elevated temperatures[J]. Research, 2020, 2020: 9089405.
12	Zhang J, Xiang Y, Lu S F, et al. High temperature polymer electrolyte membrane fuel cells for integrated fuel cell - methanol reformer power systems: a critical review[J]. Advanced Sustainable Systems, 2018, 2: 1700184.
13	Yan W R, Xiang Y, Zhang J, et al. Substantially enhanced power output and durability of direct formic acid fuel cells at elevated temperatures[J]. Advanced Sustainable Systems, 2020, 4: 2000065.
14	Guo Z B, Xu X, Xiang Y, et al. New anhydrous proton exchange membranes for high-temperature fuel cells based on PVDF-PVP blended polymers[J]. Journal of Materials Chemistry A, 2015, 3: 148-155.
15	Guo Z B, Xiu R J, Lu S F, et al. Submicro-pore containing poly(ether sulfones)/polyvinylpyrrolidone membranes for high-temperature fuel cell applications[J]. Journal of Materials Chemistry A, 2015, 3: 8847-8854.
16	Lu S F, Xiu R J, Xu X, et al. Polytetrafluoroethylene (PTFE) reinforced poly(ethersulphone)-poly(vinyl pyrrolidone) composite membrane for high temperature proton exchange membrane fuel cells[J]. Journal of Membrane Science, 2014, 464: 1-7.
17	Zhang J J, Zhang J, Bai H J, et al. A new high temperature polymer electrolyte membrane based on trifunctional group grafted polysulfone for fuel cell application[J]. Journal of Membrane Science, 2019, 572: 496-503.
18	Bai H J, Peng H G, Xiang Y, et al. Poly(arylene piperidine)s with phosphoric acid doping as high temperature polymer electrolyte membrane for durable, high-performance fuel cells[J]. Journal of Power Sources, 2019, 443: 227219.
19	赵伟辰, 徐鑫, 白慧娟, 等. 自交联聚乙烯亚胺-聚砜高温质子交换膜研究[J]. 化学学报, 2020, 78(1): 69-75.
	Zhao W C, Xu X, Bai H J, et al. Self-crosslinked polyethyleneimine-polysulfone membrane for high temperature proton exchange membrane[J]. Acta Chimica Sinica, 2020, 78(1): 69-75.
20	郝金凯, 姜永燚, 王禛, 等. 高温质子交换膜燃料电池用聚苯并咪唑/聚乙烯基苄基交联膜的制备与性能研究[J]. 电化学, 2015, 21(5): 441-448.
	Hao J K, Jiang Y Y, Wang Z, et al. Preparations and properties of polybenzimizaole/polyvinylbenzyl crosslinked composite membranes for high temperature proton exchange membrane fuel cells[J]. Journal of Electrochemistry, 2015, 21(5): 441-448.
21	Bai H J, Wang H N, Zhang J, et al. Simultaneously enhancing ionic conduction and mechanical strength of poly (ether sulfones)-poly(vinyl pyrrolidone) membrane by introducing graphitic carbon nitride nanosheets for high temperature proton exchange membrane fuel cell application[J]. Journal of Membrane Science, 2018, 558: 26-33.
22	Zhang J, Lu S F, Zhu H J, et al. Amino-functionalized mesoporous silica based polyethersulfone-polyvinylpyrrolidone composite membranes for elevated temperature proton exchange membrane fuel cells[J]. RSC Advances, 2016, 6: 86575-86585.
23	Xu X, Wang H N, Lu S F, et al. A novel phosphoric acid doped poly(ethersulphone)-poly(vinyl pyrrolidone) blend membrane for high-temperature proton exchange membrane fuel cells[J]. Journal of Power Sources, 2015, 286: 458-463.
24	卢善富, 相艳, 蒋三平. 一种燃料电池用的高温质子交换膜及制备方法: 102376961A[P]. 2012-03-14.
	Lu S F, Xiang Y, Jiang S P. A high temperature proton exchange membrane and its preparation method: 102376961A[P]. 2012-03-14.
25	姚东梅, 张玮琦, 徐谦, 等. 磷酸掺杂聚苯并咪唑高温膜燃料电池膜电极[J]. 化学进展, 2019, 31 (2/3): 455-463.
	Yao D M, Zhang W Q, Xu Q, et al. Membrane electrode assembly for high temperature polymer electrolyte membrane fuel cell based on phosphoric-acid doped polybenzimidazole[J]. Progress in Chemistry, 2019, 31 (2/3): 455-463.
26	Cheng Y, Zhang J, Lu S F, et al. High CO tolerance of new SiO₂ doped phosphoric acid/polybenzimidazole polymer electrolyte membrane fuel cells at high temperatures of 200—250℃[J]. International Journal of Hydrogen Energy, 2018, 43(49): 22487-22499.
27	Zhang J J, Bai H, Yan W, et al. Enhancing cell performance and durability of high temperature polymer electrolyte membrane fuel cells by inhibiting the formation of cracks in catalyst layers[J]. Journal of the Electrochemical Society, 2020, 167(11): 114501.
28	Oono Y, Sounai A, Hori M. Long-term cell degradation mechanism in high-temperature proton exchange membrane fuel cells[J]. Journal of Power Sources, 2012, 210: 366-373.
29	Oono Y, Sounai A, Hori M. Prolongation of lifetime of high temperature proton exchange membrane fuel cells[J]. Journal of Power Sources, 2013, 241: 87-93.
30	胡经纬, 张华民, 翟云峰, 等. 高温PEMFC的性能衰减研究与一维数值模拟[J]. 电源技术, 2006, 30(12): 977-981.
	Hu J W, Zhang H M, Zhai Y F, et al. Performance degradation studies on PBI/H₃PO₄ high temperature PEMFC and one dimension numerical modeling[J]. Chinese Journal of Power Sources, 2006, 30(12): 977-981.
31	Zhang J, Aili D, Bradley J, et al. In situ formed phosphoric acid/phosphosilicate nanoclusters in the exceptional enhancement of durability of polybenzimidazole membrane fuel cells at elevated high temperatures[J]. Journal of the Electrochemical Society, 2017, 164 (14): F1615-F1625.

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