磺酸修饰的金刚石掺杂磺化聚芳醚砜质子交换膜的制备与性能

doi:10.16085/j.issn.1000-6613.2021-2606

摘要/Abstract

摘要：

利用KMnO₄、浓H₂SO₄的氧化性及纳米金刚石边缘缺陷引入含氧官能团，得到氧化金刚石（OND）。OND在强碱条件下与1,4-丁磺酸内酯反应，进行烷基磺酸的接枝，制备带有磺酸烷基链的纳米金刚石（SND）。热重分析、红外光谱结果表明了烷基磺酸基团的成功引入，SND的离子交换容量（IEC）达到1.1mmol/g。SND与磺化聚芳醚砜（SPAES）共混后，通过溶液浇铸法制备了表面均匀平整的SPAES-SND复合膜。SPAES-SND复合膜具有较高的吸水率及较低的溶胀率、更高的氧化稳定性及电导率。其中，SPAES-SND-0.5在80℃时最高吸水率达到了75%，拉伸强度为31.3MPa，断裂伸长率为25.1%，在80℃水中的质子电导率达到166mS/cm，显示了良好的综合性能。SPAES-SND-0.5膜在80℃、100%相对湿度（RH）下燃料电池最大功率密度达到了527mW/cm²，相比于原始的SPAES膜（347mW/cm²）提高了51.9%，其优异的质子电导率和电池功率表现出较好的应用前景。

关键词: 燃料电池, 复合材料, 膜, 磺化聚芳醚砜, 纳米金刚石

Abstract:

Oxygen-containing functional groups were introduced on the surface of nano-diamond (ND) by the oxidation of edge defect carbons with KMnO₄ and concentrated H₂SO₄ to get the oxide diamond (OND). Under strong alkali conditions, ONDs were reacted with 1,4-butylene sulfonate lactone to get the sulfonic acid alkyl nano-diamond (SND). The structure of the SND was confirmed by TGA and FTIR, and the ion exchange capability (IEC) reached to 1.1mmol/g. After blending with SPAES, a series of SPAES-SND composite membranes with uniform surface were prepared by solution casting method. SPAES-SND composite membranes indicated high water absorption, low swelling rate, high oxidation stability and conductivity. SPAES-SND-0.5 displayed the maximum water absorption of 75% at 80℃, 31.3MPa of tensile strength, 25.1% of elongation at break and 166mS/cm of proton conductivity in 80℃ water, suggesting the good comprehensive properties. For the fuel cell performance at 80℃ and 100% RH, the maximum power density of the SPAES-SND-0.5 membrane reached to 527mW/cm², which was 51.9% higher than that of the pristine SPAES membrane (347mW/cm²). The excellent proton conductivity and battery power output SPAES-SND-0.5 showed its good application prospects.

Key words: fuel cells, composites, membranes, sulfonated poly(aryl ether sulfone), nano-diamonds

中图分类号:

TK-91

王盟, 刘莉莉, 李娜, 胡朝霞, 陈守文. 磺酸修饰的金刚石掺杂磺化聚芳醚砜质子交换膜的制备与性能[J]. 化工进展, 2022, 41(10): 5645-5652.

WANG Meng, LIU Lili, LI Na, HU Zhaoxia, CHEN Shouwen. Preparation and properties of sulfonate modification nano-diamonds doped sulfonated poly(aryl ether sulfone) proton exchange membranes[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5645-5652.

图/表 15

图1 SND的制备流程图

图2 ND与SND的SEM图

图3 ND和SND的FTIR图

图4 ND和SND的热重曲线图

图5 ND与SND的XRD图

图6 SPAES-SND复合膜的光学照片

图7 复合膜的SEM图

图8 SPAES-SND复合膜的FTIR谱图

图9 SPAES-SND复合膜的TGA曲线图

表1 SPAES-SND的物理化学性能

样品	IEC/mmol·g^-1	WU/%		SR/%		λ		T_s/MPa	E_b/%
样品	IEC/mmol·g^-1	30℃	80℃	30℃	80℃	30℃	80℃	T_s/MPa	E_b/%
SPAES	1.66	60	75	12.4	14.8	20.8	26	26.7	29.5
SPAES-OND-0.5	1.31	25	45	12.3	13.7	10.6	19.1	26.3	29.1
SPAES-SND-0.5	1.33	45	75	8.1	11.3	18.8	31.3	31.3	25.1
SPAES-SND-1	1.33	40	68	10.7	11.9	16.7	28.4	26	24.1
SPAES-SND-1.5	1.35	34	55	9	10.7	14	22.6	30	31
SPAES-SND-2	1.46	23	44	6.3	7.5	8.8	16.7	28	30

图10 SPAES-SND吸水率与温度之间的变化关系

图11 SPAES-SND溶胀率与温度变化关系

图12 SPAES-SND复合膜的电导率以及其质子传输情况

表2 膜的电导率、机械性能和氧化稳定性

样品	σ/mS·cm^-1		T_s/MPa	E_b/%	WL/%
样品	30℃	80℃	T_s/MPa	E_b/%	WL/%
SPAES	70	154	26.7	29.5	14.8
SPAES-OND-0.5	58	142.7	26.3	29.1	16.3
SPAES-SND-0.5	73	166	31.3	25.1	14.2
SPAES-SND-1	51	132	26	24.1	13
SPAES-SND-1.5	52	152	30	31	14.8
SPAES-SND-2	42	138	28	30	15

图 13 SPAES、SPAES-SND-0.5及Nafion112膜的氢氧燃料电池性能

参考文献 15

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